methods and devices for assessing material contents

专利摘要:
The present invention relates to methods for determining the hardness and / or ductility of a material by compressing the material as a first aspect of the invention. typically, compression is performed on multiple sides of a geological material sample in a concomitant manner. Devices and systems for performing such methods are also provided. These methods, devices and systems may be combined with additional methods, devices and systems of the invention that provide analysis of compounds contained in such samples, which may indicate the presence of valuable materials such as petroleum-associated hydrocarbons. alternatively, these additional methods, devices and systems may also function independently of methods, devices and systems for analyzing ductility and / or hardness of materials.
公开号:BR112019011944A2
申请号:R112019011944-2
申请日:2017-12-12
公开日:2019-10-29
发明作者:Smith Michael
申请人:Smith Michael；
IPC主号:

专利说明:

Descriptive Report of the Invention Patent for METHODS AND DEVICES TO ASSESS MATERIAL CONTENT.
FIELD OF THE INVENTION [001] This application claims the benefit of US Provisional Application No. ^Q 62 / 434,399, filed on December 14, 2016, entitled “Methods and Devices for Evaluating the Contents of Materials, which is incorporated into this document by way of reference.
[002] This invention relates to innovative methods for assessing material contents, including, for example, volatile substances, such as petroleum-related hydrocarbons in geological materials, as well as devices that can be used in the practice of methods and other applications .
BACKGROUND OF THE INVENTION [003] Human assessment of material content has probably been practiced longer than any written records. However, the ability to use information associated with a material to understand the properties of associated materials, such as surrounding geological formations, has been significantly developed in the past 100 years, starting with the Schlumberger brothers' revelation that electrical resistivity could be used to evaluate the structure and likely content of geological structures and thus provide a mechanism for finding subsurface materials, such as fuel and fossil deposits. Despite a significant advance, resistivity has proved to be of limited utility, especially in modern times when easily found petroleum and natural gas deposits are increasingly difficult to detect with such technology.
[004] The previous technology that involves the analysis of rock materials, such as to determine the presence of hydrocarbons in a
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2/164 geological formation, focused on the analysis of the material in fluid inclusions. Fluid inclusions are often characterized as “bubbles of fluid trapped within the host material, such as rock. These compartments within the rock or other material are usually very small, 1 to 20 microns wide. Fluid inclusions are characterized by being completely sealed and isolated from the environment, typically over a very long period of time (on a geological scale - for example, over millions of years). Fluid inclusions are believed to be the exact fluid residues associated with the rock material in the formation. As such, the content of the inclusions can provide information about the fluid composition, temperature and pressure at which a material was formed and what it can contain.
[005] In one type of typical fluid inclusion analyzes, a rock sample, usually from a sedentary rock, is crushed under a strong vacuum, and the trapping fluids that are released from crushing are analyzed, just as with a mass spectrometer . Prior to the inventions described in this document, the conditions under which mass spectrometers operate dictated how devices and methods for analyzing fluid inclusion were performed. Fluid inclusion materials have shown some utility in the discovery of hydrocarbon materials and today it is a commonly practiced method performed on materials obtained from the drilling of oil wells. However, a fluid inclusion analysis is also of limited utility due to a number of problems, as the inclusion content often does not match today's fluids in geological formation.
[006] Specific patents that describe prior inventions of the present inventor, co-inventor inventions and other inventors include US Patent No. ^Q 4,960,567 which refers to a method for
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3/164 obtaining fluid inclusion gases for analysis through mass spectrometry and US Patent No. ^Q 5,241,859 which describes a method in which material from a fluid inclusion collection is analyzed to identify collections that are rich in hydrocarbons , which can then be further analyzed, such as through mass spectrometry analysis. US Patent No 5,328,849 describes ^Q methods for mapping subsurface formations analyzing fluid inclusions in various samples by specialized I also invented devices.
[007] US Patent No 6,661,000 describes a ^Q invention made by the present inventor and co-inventors it was invented a method for analyzing liquid surface portion and in opposition to fluid inclusions, by a method wherein cuttings or other samples are directly subjected to analysis by mass spectrometry. However, one of the disadvantages of this method is the loss of gases associated with the sample due to the need to apply such relatively high vacuum levels in order to make the devices operate.
[008] The invention provides methods and devices that not only solve the limitations of these previous inventions, but also significantly expand them in terms of the applicability of the methods to various materials and associated materials, extending well beyond the simple analysis of rock samples associated with potential hydrocarbons. These and other advantages of the invention, as well as additional inventive features, will be apparent from the description of the invention provided herein.
SUMMARY OF THE INVENTION [009] In a first aspect, the invention provides new methods for determining the ability to subject a geological material to fracturing and similar processes in which hardness and / or ductility
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4/164 of a material are determined by compressing one or more samples of the material, especially on multiple sides of the sample in a concomitant manner. The sample is typically associated with a drilling operation and is often a cut. The methods typically comprise the analysis of many samples, such as 5, 10.15, 20, 30, 40, 50 or more samples (for example, 100, 250, 500, 750, 1,000, 1,250, 1,500 or more samples), usually from different locations in relation to most other samples analyzed (such as being separated by at least 22.86 centimeters (0.75 feet) vertical and / or horizontal). The invention further provides devices and systems for carrying out such methods from the first aspect. [010] These methods, devices and systems can be combined with additional methods, devices and systems of the invention that provide analysis of volatile substances contained in such samples, such as cuts, which may indicate the presence of substances in the material associated with the sample, such as oil-associated hydrocarbons (oil and / or gas). Alternatively, such additional methods, devices and systems may also function independently of the methods, devices and systems for analyzing ductility and / or hardness of materials of the first aspect of the invention, as a second independent aspect of the invention. The second aspect method typically comprises exposing the samples to one or more forces that allow or promote the release of volatile substances, capturing the volatile substances and then analyzing the volatile substances in order to identify the nature of the material composition. Such methods often include the application of a gentle force, such as a gentle vacuum step (for example, at about 10 to about 100 millibar), which allows the capture of volatile fluids in the sample without significant loss of such materials in the analytical method.
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5/164
BRIEF DESCRIPTIONS OF THE DRAWINGS [011] Figure 1 is a representation of an illustrative device / system of the invention to analyze both the compressibility of the samples and the volatile substance content of such samples through a non-selective trapping of condensable gases, a separate trapping of non-condensable gases and analysis by mass spectrometry of such compounds.
[012] Figure 2 is an example of a data set obtained by carrying out the methods of the invention in connection with the cuts associated with an oil well.
[013] Figure 3 provides another example of a data set obtained by carrying out the methods of the invention in connection with the cuts associated with an oil well.
[014] Figure 3B provides a simplified and stylized view of the selection data shown in Figure 3.
[015] Figures 4A is an illustrative plot of oil, water and oil saturated water in connection with a vertically oriented oil well.
[016] Figure 4B is a simplified representation of the key data provided in Figure 4A.
[017] Figure 5 provides yet another example of the data obtained by carrying out the methods of the invention in sections.
[018] Figure 5B provides a simplified representation of the selection data presented in Figure 5.
[019] Figure 6 is a representation of a type of geological formation associated with oil that can be identified and characterized by the use of the methods of the invention.
[020] Figure 7 provides a plot of acetic acid measurements in a geological formation against resistivity record data to identify regions associated with oil in
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6/164 sands / sandstone formations.
[021] Figures 8A and 8B provide a plot of multiple hydrocarbons at different depths to analyze the nature of oil deposits in a geological formation.
[022] Figure 8C provides a stylized representation of the data associated with a particular type of geological deposit that can be characterized by the methods of the invention.
[023] Figure 9 is an illustrative representation of mapping a region of sites using the method of the invention to characterize a larger area comprising multiple drilling sites.
[024] Figure 10 is another plot of data obtained using methods of the invention including hydrocarbon data, oil saturated water and other data elements used to identify and characterize deposits within a geological formation at different depths.
[025] Figure 10A is a simplified representation of the key data patterns in Figure 10.
[026] Figure 11 provides a representation of two data sets for different formations / sites that can be differentially analyzed by the methods of the invention.
[027] Figure 12 provides an illustration of a well site device for analysis of fracturability / cut compression allowing real-time / near real-time targeting of a side well.
DETAILED DESCRIPTION OF THE INVENTION [028] The invention described in this document provides several types of devices and methods for analyzing the contents of hard mineral based materials, such as rock samples taken from geological formations. A key use of these methods and devices is
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7/164 the analysis of oil well drilling cuts for the contents of certain compounds in such cuts or that can be obtained from such cuts, which, in turn, provide information about the geological material associated with the cuts. However, the methods and devices of the invention are not limited to such applications and adjustments and can be applied to other adjustments, as will be discussed further in this document.
[029] In a primary aspect, the invention described in this document provides a method for analyzing volatile substances in a material comprising the steps of (a) providing an analyzable sample of a material containing an analyzable amount of one or more volatile substances, (b) allowing the release of fluid (for example, gas) containing the volatile substances in the material, (c) optionally subjecting the sample to one or more forces to assist in the release of the fluid, (e) optionally trapping the fluid by contact with a means, in an analyzable amount (an aliquot), (d) optionally isolating the fluid from the material, (e1) applying energy or one or more forces to the aliquot in order to cause the volatile compounds in the aliquot, if present, form other chemicals (gas (or gases) treated with energy) in a predictable manner and / or (e2) release volatile substances from the aliquot as fluids released from imprisonment o a predictable sequence and (f) analyzing the chemistry of one or more fluids released from entrapment and / or energy treated fluids.
[030] The inventive methods described in this document can be practiced with any suitable material containing any suitable number and / or suitable number of any suitable type of volatile substances. Suitability in this respect means that volatile substances are amenable to analysis by the methods and / or devices of the invention, which can be determined by the principles
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8/164 described here or through the application of routine experimentation. A volatile substance in the context of the invention is a material that will take the form of a gas under the conditions under which the method is carried out. Conditions relevant to whether a material is in the form of a gas at a particular time include the pressure under which the material is at the moment. In one aspect of the invention, at least one volatile substance is released from the material at atmospheric pressure. In another aspect, at least one volatile material analyzed by the method is released from the material under a vacuum (a pressure less than atmospheric pressure - that is, a pressure less than about 760 Torr or 1.013x10 ⁵ Pa) or significantly more of the material is released under a vacuum at atmospheric pressure (such as at least about 2 times, at least about 3 times, at least about 5 times, at least about 10 times, at least about 20 times, at least about 30 times, at least about 50 times or at least about 100 times atmospheric pressure).
[031] In a particular aspect, the method includes analyzing at least one volatile substance that is released from the material under low vacuum conditions. Low vacuum conditions mean pressure conditions in the range of about 760 to about 25 Torr or 1x10 ⁵ to 3x10 ³ Pa (in this document, each disclosure of an amount modified by modifiers, such as “about, must be interpreted as simultaneously providing the corresponding exact reveal, and each reveal in a range should be interpreted as revealing each unit of the same order of magnitude as the end points of the range, for example, a reveal in the range 1 to 5 should also be interpreted as revealed numbers 1, 2, 3, 4 and 5 individually). In another exemplary aspect, the method includes the step of analyzing at least one volatile substance that is released below, but close to 1,000 millibar, such as about 40 millibar at
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9/164 about 950 millibar, for example, about 50 millibar to about 900 millibar, about 100 millibar to about 800 millibar, such as about 150 millibar to about 750 millibar, or any combination of such points. low and high end.
[032] In another context, the method also includes, or alternatively, analyzing at least one volatile substance that is released from the material under medium vacuum conditions. Medium vacuum conditions mean pressures from about 25 Torr to about 1x10 ^-3 Torr (3x10 ³ to 1 x 10 ¹ Pa). In another aspect, the method includes analyzing at least one volatile substance that is released from the material under a pressure of about 50 millibar (for example, applying one or more pressures of about 20 to 80 millibar, such as about 30 to 70 millibar) millibar) and, in yet another aspect, the method comprises performing an analysis in an aliquot obtained by extracting at one or more pressures in the range of about 30 millibar to about 10 millibar, such as about 25 millibar to about 12 millibar , for example, about 20 millibar to about 15 millibar, or any other combination of such low and high end points.
[033] In another aspect, the invention also includes analyzing at least one volatile substance that is released from the material under high vacuum conditions. High vacuum conditions mean about 1x10 ^-3 to about 1 x10 ^-9 Torr (1 x1 O ' ¹ to 1 x10 ^-7 Pa). In another aspect, the invention includes analyzing at least one volatile substance released under vacuum pressures of less than about 5 millibar, such as less than about 2 millibar, such as less than 1 millibar. For example, in another aspect, the invention comprises analyzing at least one volatile substance released under vacuum pressures of about 1x10 ^-2 millibar or less, such as about 1x10 ' ³ to about 1x10' ⁹ millibar.
[034] In still other aspects of the invention, the method does not comprise the application of high vacuum (such as those described
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10/164 above), which, in this respect, distinguishes such aspects of this invention from prior art methods which include or are dependent on high vacuum application to carry out the analysis of materials. In still other aspects, the practice of the method of the invention has no application of any high vacuum or any medium vacuum in the release of volatile compounds. This distinguishes these aspects, among other things, from prior art methods, such as many forms of fluid inclusion analysis, which typically require the application of high vacuum and / or medium vacuum.
[035] The material can also be any material that can be suitably subjected to the methods of the invention. In a typical context, the material is a geological material, such as rock material, mud, or soil, or a by-product of drilling, especially drilling mud or a drilling cut. In the context of this invention, terms such as "cuts and" drilling cuts "mean fragments of rock that are brought to the surface in a drilling operation (such terms are generally understood in the art). Typically, drilling cuts are rocks that are kept separate from the drilling muds in a stirring table operation or similar separation process. Drill cuts can be of any suitable size. The size of the cuts produced in a well will depend on several factors including the geological material that is drilled and the drill bit used, with more modern drill bits often forming smaller cuts. The particle sizes of the cuts can be, for example, as small as about 5 microns (for example, about 10 microns or more, about 20 microns or more, about 25 microns or more, about 50 microns or more , etc.), but typically the slices will have particle sizes of at least about 100 microns, such as at least about 150 microns or at least
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11/164 about 200 microns (for example, about 250 microns or more), and can be significantly larger, such as up to about 7.5 mm (for example, about 6.5 mm or less, about 6 mm or less or about 5 mm or less). Commonly, cuts that typically have a particle size of between about 0.5 mm to about 1 mm and about 5 mm to about 6 mm are used in the methods of the invention. However, in a particularly unexpected aspect of the invention (as exemplified elsewhere in this document), the method was carried out using rather small cuts that were produced in a witnessing process, which are significantly smaller in size than the standard cuts obtained in production or exploration of oil. So, for example, the method can be carried out with cuts of about 100 microns to about 5 mm, about 50 microns to about 10 mm, about 25 microns to about 7 mm, about 25 microns to about 12.5 mm, about 50 microns to about 6.5 mm, about 0.2 mm to about 6 mm, about 0.25 mm to about 5 mm or about 0.5 mm to about 5 mm. These are exemplary strips, and these endpoints of any of these strips can be interchanged with the endpoints of any other stripe to create other suitable strips on which other exemplary methods of the invention focus.
[036] “Drilling mud,“ mud or “drilling fluid in the context of this invention refers to a material that is distinguished from cuts. Drilling mud is the material that is at least initially introduced into a well site and used by the operator of a drilling operation to perform one or more functions including providing hydrostatic pressure to prevent formation fluids from entering the well hole, maintaining the temperature and / or “cleaning of the drill bit (or at least preventing overheating and / or obstruction), maintaining the structural integrity of the unfinished well and / or
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12/164 assisting in the transportation of drilling cuts. Drilling muds will contain materials such as bentonite, barite or hematite, and can be water-based or oil-based. Sludge is often dense and thixotropic material, meaning that it becomes more fluid with agitation. The nature of the drilling muds and the differences between drilling muds and cuts will be understood by those skilled in the art.
[037] In a specific context, the material is rock or mud material that is associated with exploratory drilling or production drilling for oil, natural gas or related materials, any materials obtained from other activities, such as exploratory and production drilling for economical mineral deposits and geothermal energy, could also or alternatively be used in the practice of the methods of the invention. The material can also, or alternatively, be from sources other than natural geological formations or other geological samples related to non-oil or even biological samples, such as teeth, bones and the like (for example, food or biomass of any type of organism viable or non-viable living). In this regard, the methods of the invention can be applied in various forensic and / or intelligence applications, to determine the impact of processes on materials, the historical source or modulation of materials and / or, for example, the origin of materials and other information about the nature of such materials. For example, in another context, the material is construction material, such as material used in the construction of commercial buildings, bridges, roads, construction sites, antiques and the like. The methods can also be applied to other artificial materials, such as ceramics and other types of materials used in the manufacture or construction of other devices and structures, such as semiconductors.
[038] In one aspect of the invention, samples selected for
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13/164 analysis on the performance of the method comprise, are substantially comprised of (i.e., more than about 20% of the samples are), are primarily comprised of (i.e., more than 51% of the samples are), consist essentially of de (are comprised of, at a level where the amount of non-conforming material does not impact the nature of the total sample or set of samples) or consist entirely of material that does not have substantially relevant fluid inclusions (“RFIs). "Relevant fluid inclusions or" RFIs in the context of this invention refer to fluid inclusions that (1) contain one or more materials that are indicative of the presence of a substance in the material (at least in the inclusions), such as oil or substances related to petroleum (for example, organic acids, hydrocarbons and the like, such as acetic acid) and (2) the presence of such materials reflects the present condition of the material (in terms of the presence of the target substance). Samples may not have relevant fluid inclusions for several reasons, such as relevant fluid inclusions may never have formed in the material (for example, shallow, unconsolidated, young sandstone oil reservoirs in the Gulf of Mexico) or inclusions of relevant fluids may have been destroyed by natural and / or human processes (for example, meteorite impact or drilling with polycrystalline diamond compact drill bits (“PDC)). As indicated elsewhere, fluid inclusions will often contain old fluids that often do not reflect the present fluid content of the material. In certain cases, relatively “young fluid inclusions can form in a material or older fluid inclusions can be filled with relatively“ young material that is present in a material. Such fluid inclusions can be classified as RFIs. Non-relevant fluid inclusions (“NFIs) can also provide relevant information for
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14/164 understanding of the material, but they are less evident in relation to the fluid content of the material than RFIs. Not having substantially RFIs means that less than 0.000005% of the sample volume consists of the target substance (for example, oil) or fluid inclusions related to the target substance (for example, only about 0.05 ppm or less of the sample volume consists of oil or one substantially relevant to oil). In some cases, the invention is practiced in which the amount of RFIs is even less, such as 0.025 ppm or less, about 0.02 ppm or less, or even about 0.01 ppm or less of the sample volume. made up of fluids containing target substance or relevant to target substance (in still other aspects, the amount of RFIs in the sample is even less, such as about 20 parts per trillion of the sample volume or less, about 10 parts per trillion sample volume or less, about 5 parts per trillion of the sample volume or less, or even about 1 part per trillion of the sample volume or less. In still other aspects, the sample or some part of the sample (samples ) analyzed does not contain any detectable amount of RFI. In some cases, the sample may contain more volume of fluid inclusions, however, fluid inclusions will be known as not relevant in the sense that there is information that informs the technician. technique that the material in the fluid inclusion is not indicative of the fluid content of the material (for example, the inclusion is indicative of the presence of oil, but it is known from the perforation that the material content reflects little or no oil being present in the material). In certain respects, the material and / or the sample are or comprise a material that does not have materials that will form a sufficient quantity, size or type of inclusion to be relevant, such as many unconsolidated / young shales or sands, which commonly do not have material that is hard the
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15/164 enough to form sufficient inclusions that can provide detectable levels of RFIs even if the target substance is present in the material. It is important to understand that the term “target in this and other contexts to describe aspects of the invention can mean, but does not always mean, a specific substance that is expected to be present or that is sought by analytical methods of the invention. Thus, for example, the “target may be one or more unknown materials that are in a material, such as one or more substances that are included in drilling cuts or other geological material, but that have no known composition prior to analysis.
[039] In another aspect of the invention, the samples analyzed and / or the material comprise a low number of RFIs. For example, in a particular facet of the invention, the sample is a collection of cuts in which less than about 20%, less than about 15% or about 10% or less, such as about 5% or less of the cuts comprise RFIs.
[040] In other respects, materials or samples with fluid inclusions may be included intentionally and will be commonly included in the sample and / or material, and in such cases, the method may optionally and additionally understand, as discussed below, the performance of other methods in materials containing fluid inclusions removed from the site and / or included in the samples.
[041] The material and / or samples will typically include cracks, fractures, pockets, cracks, etc., which contain target materials of interest, such as volatile hydrocarbons. Such cracks, fractures, etc. (collectively referred to herein as “target substance pores or“ TSPs) will often and desirable contain the target substance or material relevant to the target substance (for example, such as organic acids and / or hydrocarbons that are
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16/164 indicative of the presence of oil) which are also, in some cases, (1) present in relevant quantities in the material (either in fluid form or are absorbed or adsorbed to the material), rather than material which are artifacts of existing conditions previous, as is the case with many NFIs, (2) are exposed to the surrounding environment in some amount (such as being contained in a pore in the material that is exposed to the surrounding environment) (in other words they are not completely isolated from the environment as it is the case with fluid inclusions) or (3) can be characterized by the fact that they satisfy both (1) and (2). A “pore fluid in the context of this invention means a substance that is ordinarily a liquid or gas in association with the material, contains one or more volatile products and is found in a TSP and meets conditions (1), (2) or (3 ) of the previous sentence. In some aspects, the invention is characterized by analyzing one or more samples containing an analyzable amount of pore fluid (or fluids) and / or by analyzing one or more samples containing an analyzable amount of a pore fluid-related substance.
[042] In a number of particular ways, the material consists of, understands or is substantially comprised of a geological material that has not experienced significant enough burial diagenesis to have formed fluid inclusions. “Substantially understood in the context of this invention means that substantially a majority, such as at least 65%, more often at least 75%, such as at least 80%, at least 85%, at least 90% or even at least at least 95% of the referenced material or composition is comprised of the component in question. In particular aspects, the material consists of, is comprised of or is substantially comprised of “young sands. In the context of this invention, “young sand means
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17/164 recent sediments from the Miocene and Plyocene Periods (for example, 0 to 5 million years old). For such sands that are buried about 3,048 meters (10,000 feet) below surface level or less in a tectonically quiet area (an area with relatively less earthquakes), RFIs will typically not be present or will be substantially insufficient, as described elsewhere in this document.
[043] In yet another aspect, the sample and the material comprise a material of “little permeable carbonate. "Low-permeable carbonate in the context of the inventive methods means a material that comprises a substantial carbonate portion (for example, at least about 90% of the material is comprised of one or more carbonates) that exhibits low permeability (for example, about 15 millidarcies or less, about 10 millidarcies or less or about 5 millidarcies or less). In one aspect, the material is a material that is not suitable for traditional Sw analysis, due to the fact that electricity cannot flow sufficiently through the material to generate appropriate signals required for Sw analysis based on traditional resistivity. The methods of the invention can, also or alternatively, be applied to similar types of materials of other settings that have similar types of resistivity, permeability and / or conductivity problems.
[044] The material is typically obtained in an analyzable sample or presented in an analyzable sample. In a general sense, an analyzable sample can be any sample that has the necessary characteristics that allow it to be analyzed using the specific conditions of the inventive method to be practiced with the material. Persons skilled in the art of this invention will have the ability to select such materials based on the
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18/164 other conditions of the method, in the teachings provided here, especially in view of routine experimentation, and in other known principles. For example, the sample size must be large enough to provide enough material to be analyzed. In addition, the sample is typically manipulated in order to preserve the material in the sample to allow volatile substances to be released from it by applying the force (forces) to be applied in carrying out the method of the invention. Other conditions and resources for sample collection, storage and / or manipulation can be selected in order to maintain the structural and / or chemical stability of the sample and volatile compounds contained therein. The sample should also typically be sufficiently free of materials that can interfere with the analysis. For example, the sample is typically collected and maintained in such a way that it is substantially free of material from other sources that can “contaminate the sample by causing it to provide false information about the location from which it is taken and its contents.
[045] In yet another aspect of the invention, the sample is obtained from a process that comprises the use of an oil-based slurry. In general, drilling muds can be water-based or oil-based. Oil-based sludge can create difficulties for analytical methods, such as the inclusion analysis methods known in the prior art. These methods typically require the application of high heat and / or vacuum, such as, for example, in a vacuum oven, applied over a long period in order to deal with samples obtained with oil-based mud drilling processes or risk interference from the oily base of the mud and / or the oily material used to wash the samples. Such problems also exist in relation to non-fluid inclusion analysis methods, such as any other inventions. Methods in which high temperature and / or
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19/164 vacuum are applied to remove oil-based sludge they may suffer from the problem of also removing any endogenous hydrocarbons, organic acids and / or oil. The ability to analyze such samples with the methods of the invention is yet another advantageous aspect of the inventive methods described herein. Samples, also or alternatively, can be obtained from water-based mud drilling operations, and in some cases (as exemplified in this document), samples can be obtained from a site that has undergone both drilling of oil-based mud for drilling water-based mud.
[046] As discussed elsewhere in this document, samples can be sealed on or shortly after collection. In such components, about 0.5% to about 5% of the sample volume can consist of the target substance or target-related substance. For example, about 0.75% to about 3.5%, such as about 0.8% to about 3%, about 0.9% to about 2.75% or about 1% to about 2.5% of the sample volume may consist of the target substance (or target substances) (for example, C5-C10 petroleum hydrocarbons) and / or materials related to the target substance. These amounts of target-related substances are typically higher than the amount that would be found in materials that have only such target substances or materials related to the target substance in fluid inclusions.
[047] The quantity of material collected or supplied may be excessive in relation to the quantity that may be the subject of analysis at any time in order to provide assurance that there will be enough of the sample material to perform repeated executions of the method, etc. Any suitable amount of material can be used. A typical sample can be in the order of about 100 mg, but it can be as low as about 1 mg, about 10 mg, about
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20/164 of 25 mg, about 50 mg, or about 75 mg. The maximum sample size is often determined by the sample container size and / or the capacity of the mass spectrometry analytical component of the device used in the method, if present. However, under the right conditions and using the right type of device, samples as large as 1 g, 5 g, 10 g or even larger may be suitable for analysis.
[048] Typically, the sample will be collected from material that has a relatively known location. The location will usually include approximate depth information in addition to the longitude and latitude coordinates. Often, the site can be a site of interest in oil or mineral exploration, such as an expected or known oil well, an oil well that was previously considered non-productive, or a mineral mine, such as a gold mine.
[049] In another aspect of the invention, the sample is a fragment of a core sample. Core samples are commonly generated in oil exploration and related processes and are well understood in the art. The analysis of core samples is considered important because of the preservation of oil or other target substances in the material. However, the process of analyzing core samples is often very time-consuming. Advantageously, the methods of the invention can be used, for example, to analyze the core sample fragments much more quickly, for example, by assessing the hydrocarbon content of such core sample fragments.
[050] In most aspects of the invention, the sample is collected, stored and supplied in a container. Such a “sample container can be any suitable type of container for holding samples in the context of the method to be performed. In some aspects of
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21/164 invention, the sample is either directly analyzed from the sample container or is placed in a different analysis container before analysis. Sample containers may include or have certain features that are advantageous in performing some of the techniques described in this document. Typically, the sample container is enclosed and usually at least partially isolated from the environment (and preferably substantially, if not completely or essentially completely, isolated from the environment), in order to keep some of the volatile compounds in the sample over time, allowing other steps of the method to be performed for a period of time after collection (and storage). In specific aspects, the sample container has the ability to preserve a majority of the volatile substances in the sample at the time of insertion into the sample container (and in some cases, more than a majority, such as about 65% or more, about 70% or more, about 75% or more, about 80% or more, about 85% or more, about 90% or more, about 95% or more, or even about 99% or more (e.g. 99.5%, 99.9% or more) of the original volatile products are kept) for a desired period of time (which can be, for example, 1 week, 2 weeks, 1 month, 3 months, six months or even a year or more). The maintenance of volatile products in such occurrences can be under typical, limited or special conditions (for example, refrigeration or freezing may be required or desirable in some cases, but in many cases the samples can be kept under a wide range of temperature conditions without much extra care). In other respects, the sample container only needs to be able to maintain a sufficient level of volatiles to be tested in the method, which can be less than 50% of the volatiles in the sample when the sample was loaded into the sample container . In some
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In 22/164 cases, the amount of volatile products is greater than about 65%, such as about 75% or more, about 80% or more, about 85% or more, about 90% or more, about 95% or more, about 97.5% or more, about 99% or more, or even about 99.5% or more (such as about 99.9% or more) of the volatile products present in the sample when placed in the sample container are kept. In some respects, samples can be kept in the container with one or more substances that reduce the probability of biological activity that can reduce the probative value of the sample.
[051] In one aspect, the sample container comprises a feature, such as a fence, wall, lid or the like (hereinafter simply referred to as “fence, unless the context otherwise requires or unless explicitly determined otherwise). otherwise), which is selectively penetrable by a flow channel device, such as a needle, so that volatile substances in the container can be released when the sample container is penetrated without significant loss of such volatile products. Thus, the seal is typically of a material and construction so that it does not release volatile products by puncture or other formation of passage through it to provide means for releasing the volatile products to the other components of the system used to carry out the method. Methods for determining the integrity of the seal can optionally be used in the method, as described below in relation to the deformable portions of the container. Loss or contamination in the container from the punch or other type of opening or passage through the seal will typically be undetectable or will be of very small amounts (for example, less than about 1%, less than about 0.25 %, less than about 0.1% or even lower quantities).
[052] In another aspect, the methods, systems and devices
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23/164 can be practiced with containers that comprise a puncture-free method / step and / or puncture-free component / system or device to provide access to sealed volatile substances within a sealed sample container. For example, in one facet, the invention provides a system and method in which a sample container, such as a sample tube, has the ability to be selectively open to the system, such as facets in which the sample containers are sample within an involved self-sampler and the remaining portion of the system enters fluid communication with the sample / container by positioning the sample tube in a position where the open end of the sample tube / container is allowed to interface with an entrance to the rest of the device / system, typically, for example, by means of an automated vacuum sealing connector, which can, for example, cause an O-ring to be clamped between the system and the open sample tube, sealing, thus, the tube to the system without any puncture or any needle pass. In this type of facet, the system / device does not allow significant loss of sample tube contents in the system, as described elsewhere in this document in relation to other sample containers (for example, less than about 5%, less than about 3%, less than about 1%, less than about 0.5% or even less than about 0.2% of the content is lost after being placed in the sample container, in this case system / device).
[053] In another aspect, the sample container also includes, or alternatively, sufficient space beyond that which is occupied by the sample itself, so that some portion of the container can be filled with released volatile products. Accessible space is also often provided for the needle or other channel forming member or device to allow access
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24/164 to the sample container, in aspects where a sealed container is provided. Thus, typically about 2 to 20%, such as about 3 to 15%, for example, about 4 to 10% of the container, when sealed, is left as an open space providing space for gas and also for the entrance of the device flow channel. The container may have more open space before the seal to also provide space for the seal (for example, about 5 to 25% of the container may be designed to be opened before the seal).
[054] In yet another aspect, the sample container also comprises, or alternatively, a portion that is designed to be modifiable under certain conditions, such as being deformable under mechanical pressure, so that the force of any sufficient mechanical pressure applied to the sample container can be transferred to the sample and thus cause or increase the release of volatile substances, preferably without disturbing the structural integrity of the sample container in any way that would cause the release of any quantity or any significant quantity of products volatiles that are released into the container (for example, less than about 1%, less than about 0.25%, less than about 0.1% or less than any detectable amount of volatile products is released at from applying force to the deformable portion of the sample container) and / or causing contamination of the container space (and volatile products contained therein) with substances from the surrounding atmospheric environment (such as air in the laboratory). The method may comprise monitoring the pressure in the vessel or pressure in the vessel as connected to the analytical device, as a measurement to ensure that no leakage and / or contamination is occurring due to leaks. Other methods could, also or alternatively, be carried out to ensure that such leaks from the container are not occurring, such as
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25/164 analyzing compounds in the environment around the container using conventional methods. As noted above, such techniques can also be applied to ensure the integrity of other aspects of the sample container or other elements of the system that are used in the practice of the methods.
[055] In typical and preferred aspects, the sample container is specifically adapted for use in one of the inventive devices described elsewhere in this document to carry out the various methods of the invention. Features that the sample container will typically comprise in order to be suitable for use in such devices include (1) a penetrable seal that is comprised of a seal material that is both (a) inert to and (b) is at least substantially, if not entirely, impervious to the sample material and volatile materials contained therein (by “inert, it is understood that the material will not react chemically with volatile materials and sample materials and does not generate volatile products under the conditions in which the method is carried out, thus modulating the analysis) and (c) it is adapted in shape and size to seal the body of the container in relation to the transmission of gases and other materials that can partially or entirely interfere, corrupt or decrease the efficiency of the analysis, and preferably, and (2) a body comprised of a material that can be subjected to forces to be used in the method to extract volatile materials, which , in preferred aspects, includes crushing the sample container (and materials within the container) (for example, the sample container body comprises or is composed of a material that is crushable under the force used by the device, allowing the sample from the material is also crushed while releasing the volatile materials from the sample into the container, the sample container being constructed in such a way that it is not compromised and
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26/164 so as not to lose its sealing properties when being crushed as discussed elsewhere). The inert material principle discussed in this paragraph also typically applies to all elements of the sample container and to other elements of the system used in the practice of the method. Thus, for example, piping, trapping devices and analytical devices incorporated into the system will be similarly selected based on being inert in relation to the sample and volatile products that are expected to be present and subjected to analysis.
[056] In certain aspects, the method comprises multiple crushing cycles, such as crushing the sample container by applying crushing and / or squeezing or compression forces, typically from different directions. In yet another step, the method comprises restoring the container, at least partially, to its original shape after the application of a crushing step or multiple crushing steps. The step of crushing or compressing samples can be carried out at any appropriate time. In one aspect, the crushing step is carried out after the application of other forces that promote the release of one or more volatile substances from the sample. In another aspect, the step of crushing or compressing the sample is carried out before applying other forces to the sample to promote the release of volatile products, such as applying pressure to the sample. In still other aspects, as described elsewhere in this document, the step of compressing the sample can be carried out regardless of the extraction or release of volatile compounds (and vice versa).
[057] The preferred sample container is at least partial or relatively flexible in design to allow the capture of a variety of sample types under a variety of conditions. The methods of the invention can vary considerably in terms of
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27/164 pressure, temperature, gas content and other relevant factors. The sample container and other elements of the system are typically selected to have the ability to operate under a wide variety of such conditions. Pressure conditions are provided elsewhere in this document that can help to characterize such suitability. The temperatures used in practicing the methods of the invention can also vary considerably, especially when high temperatures are used to remove material and freezing is used as a trapping method. In this regard, the general system, including the sample container, can see temperature ranges from about -273 / -270 degrees C ("degrees C in this document means degrees Centigrade) to about 500 degrees C, such as about -195 degrees C at about 200 degrees C. In many ways, the temperature in the system will not exceed or even possibly reach 100 degrees C. In other ways, the temperature in the system will not exceed or possibly not reach 50 degrees C, particularly in the sample container. By remaining at such temperatures, more accessible materials can be used in the practice of the method. Also, these extreme temperatures may not be reached in all parts of the device. For example, heat can be applied to the sample container, but freezing temperatures can only be applied to the trapping device.
[058] The flow channel or needle is used to penetrate or otherwise form a passage for the flow of gases from the sample container (or, more particularly, in typical embodiments, a needle is used to penetrate a sealing component of the or associated with the sample container). In embodiments that include the use of a needle, the needle size is typically selected so that it provides sufficient flow of volatiles from the sample container to the rest of the system, but is not so large as to
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28/164 cause the seal to puncture and release the seal material (or other portion of the container) inside the sample container. A needle used in the methods in this document can have any suitable configuration of inlets (holes) to receive the gas. A single orifice, placed on the side, or two orifices, placed on each side of the needle, are typical. The lateral placement of the needle can help to ensure that the needle entry does not become obstructed after passing through a seal or side wall of the container. A type 5 needle (by Hamilton), for example, provides such a balance with the exemplary devices described in this document.
[059] As noted above, sealed samples can be stored for significant periods of time and still be successfully analyzed using the methods of the invention. Some volatile products can be trapped in hermetically sealed empty spaces in solids, such as fluid inclusions in rocks. In some modalities, such volatile products can be analyzed years or decades after the sample is collected. Volatile products hermetically sealed in the solid can be released by crushing the solid or thermally heating the solid until the void-filled voids are decrepit.
[060] Other volatile products can readily escape their solid, liquid or gaseous host. Such volatile products include oil, water and gas in pores in drilling or core cuts or within the drilling mud used by the well. It will typically be desirable for such solid or liquid samples to be sealed as quickly as practically possible to allow for more representative analyzes of oil, water and gas within the Earth. As demonstrated and discussed elsewhere in this document, the methods of the invention can be practiced with old materials
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29/164 exposed, in which some loss or even a significant loss occurred, but better results are often obtained with samples that are sealed within a short time of the sample reaching the surface or being exposed to atmospheric conditions that would allow the release of such relevant substances. [061] In one aspect, inventive methods are practiced without applying a significant vacuum or pressure to the sample before the method is performed. The prior inventions and other prior art methods will often apply significant vacuum or pressure and / or significant temperature to samples prior to analysis of the materials. The lack of such a step in certain aspects of this invention is yet another way in which such aspects are significantly distinguishable from the prior art.
[062] Although sample containers that can be crushed or otherwise compressible are often preferred, a wide variety of sample containers may be suitable for samples that do not require mechanical breakage (for example, glass bottles, graphite tubes or other containers that are waterproof and inert) in the practice of certain aspects of the inventive methods. So, for example, if there is no need for mechanical breakage, glass vials or sealed metal tubes can be used as sample containers. Various hoses made of rubber or other polymers can also, or alternatively, be sufficient if they can be hermetically sealed. Even Mylar or plastic bags can be sufficient for some applications. In some aspects of the invention, containers can also comprise or be primarily, almost entirely or entirely made of carbon fibers. In fact, any container that can be hermetically sealed may be sufficient, depending on the nature of the material to be
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30/164 bulk being captured.
[063] Commonly, the sample container comprises a septum or a cap (for example, a cap of nitrile or synthetic rubber) that is inert and through which a suitable flow channel device, such as a needle, can readily be passed while maintaining the integrity of the seal. In such aspects, volatile products purged from the sample will enter the entry lines through the needle. Such sample container elements are optional. In another exemplary embodiment, the sample container is sealed using a compression fitting that can be automatically applied, with subsequent rupture of the sample container to release volatile products at the entrance to the system. Another approach that may be more appropriate in some cases would be to insert the entire sample container into an airtight chamber that is attached to the inlet system, followed by the subsequent rupture of the sample container to release volatile products. The sealed sample container could be automatically introduced one at a time through an appropriate port, or an individual sample or multiple samples could be pre-loaded and sealed in part of the intake system.
[064] If the sample needs to be crushed and is outside the inlet system connected by a needle through a septum, lid or other means, such as a remotely controlled compression fitting, it may be desirable that the container can be crushed without leakage, and that any movement of the sample during crushing does not break the seal between the sample container and the inlet system. The selection of parameters for sample containers, seals and other elements of the device and compression / crushing methods in general will be selected so that a seal is maintained and there is no loss
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31/164 undesirable effects of volatile products or material or contamination thereof. A brass cylinder sealed at the bottom with a neoprene plug and sealed at the top with a nitrile cap, for example, can be a suitable sample container. However, other metals and other sealing methods can be employed in the sample container or systems / methods of the invention. For example, a brass rod could be partially pierced to produce a sealed vessel at the bottom, thus eliminating the need for the neoprene plug. Similarly, the cap could be manufactured from a variety of compounds, however, Nitrile has very good sealing properties for hydrocarbons and for most other volatile products.
[065] It is typically important that if a cap is used to seal the sample container, it can be hermetically sealed to the sample container body. This can sometimes be achieved by simply making the diameter at rest of the cap sufficiently smaller than the diameter of the tubes so that the cap needs to be extended over the tube or fitted to the tube that forms the body of the sample container . Extending this way itself can typically result in sufficient sealing. If not, then additional methods must be employed to affect a thermal seal between the cap and the tube, such as applying a compression device, such as a hose clamp or plastic clamp, or a metal ring that has a larger diameter. than the tube, but smaller than the diameter of the cap when covering the tube, around the outside of the cap. Other methods of sealing the cap to the tube may include applying glue, or epoxy, or wax, or grease, or some other sealing substance between the cap and the tube. It is also possible, instead of using a cap, to use a septum crimped to the top or other part of the sample container for a needle to pass through, or even a polymer plug, such as a neoprene plug, used to seal
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32/164 the bottom of the sample containers. A sample container that is attached to the inlet system by an external compression fitting, or some other means, such as a screw fitting, as in a hose (or a screw cap), which is larger than a needle, can form a channel or flow path between the sample container and the inlet system. Such a sample container adapted to be in direct material communication with a larger diameter inlet system can be sealed using a wide variety of sealing materials including metals, polymers, glass, even such exotic media as a salt plug or sugar, glue or other adhesive or sealant material. The sealing material will typically produce an airtight seal after the sample is captured until the moment it is broken and must be receptive to rupture after fixing to the entry system. Similarly, sample containers that are loaded entirely into the inlet system will, in general, be hermetically sealed after loading the sample and will usually maintain this airtight seal until it is broken in some way or made permeable to the substance (or substances) of interest. at the appropriate time within the entry system.
[066] As exemplified by the previous passages, it can be, in some aspects, advantageous and / or important that the general system (sample container, inlet or other elements of the system) is configured and constructed so that the general system maintains its integrity , particularly in relation to the sample and volatile products released from it, by applying any forces applied in the method, such as any crushing force. An example of such an approach is the use of a billet associated with the needle, as exemplified elsewhere in this document. In aspects where the application of a crushing force causes parts of the sample container to move, become deformed
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33/164 or become displaced in another way, such movement may allow the hole through which the needle passes to become enlarged, which may, if not resolved, allow for undesirable release of materials and / or contamination of the sample system / container . A billet associated with the needle, such as by using a compression spring placed around the needle, forcing intimate contact between the billet and the cap or seal, can guarantee the user that any such expanded hole formed in the cap or seal does not yet allow such release or contamination. However, other approaches can be similarly used to ensure that the sample container / entire device system maintains the integrity of the material, depending on the configuration of the device and sample container (and method steps) and any volatile products released, and the invention is not limited to this billet / spring approach. For example, if a high temperature is applied to the sample container, the sample container and inlet can be configured and compounded so that the application of such a high temperature does not allow the formation of any cracks or openings that would similarly allow contamination or undesirable release.
[067] In one aspect, crushing a sample container and the sample contained therein is used to assess the ductility (and / or porosity) of the sample and, correspondingly, the material. In a method in which a material of relative standard strength (in terms of crushability under a relatively fixed amount of crushing force) (such as using the same material quality in the same thickness, etc., within very small variations ( for example, about 10% variation or less, such as about 5% variation or less, such as about 1% variation or less in thickness and other relevant characteristics) is employed with a standard sample measurement (again , given
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34/164 ability to have similar variability in quantity), the amount of deformation of the container, also reflecting the sample's crushability, may be correlated to the material's resistance and / or to the material's ductility (and / or material porosity). Such methods can be advantageous in that the method is carried out in connection with oil fracturing or similar methods in which the ductility of the material is a very important resource of the material.
[068] Mapping the ductility of the samples versus the drilling depth measured in a vertical well, or in a horizontal well, can provide information as to which sections of the rock are most likely to have a low risk of fracture failure. Fracturing failure occurs when rocks that have been hydraulically tracked do not have sufficient mechanical strength to keep the induced fractures open after the injection of a support material, usually sand. This aspect of this invention, therefore, is called “fracturing, as an advantage of this invention aspect is to allow practitioners of the method to map those sections of rock drilled by an oil well that will maintain open fractures after fracturing and injection of support material. This can be especially critical near the unfinished well, since, if fractures near the unfinished well do not remain open, none or only a very small amount of oil and / or gas can be produced.
[069] An embodiment of this aspect of the invention is to measure a container, such as a sample tube as described in this document loaded with cuts, after tightening to a known force, with a micrometer or other appropriate measuring device. Such a method can be performed manually after the sample has been squeezed, or it can be done automatically as part of the analytical process using a device, such as a
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35/164 linear translator that mechanically monitors how far the pneumatic pistons are extended after the sample tightening is complete, or a device, such as a laser telemetry instrument, also to measure the full length of the air piston, or other means of tightness, after the sample is fully tightened to its final thickness.
[070] Real-time measurement of the tightening process by an appropriate measuring medium allows additional information to be collected that provides useful and necessary information for the design of an ideally successful fracturing work. This includes measuring how the air piston or other tightening means deforms the sample as a function of time and / or the amount of pressure applied. Sample deformation can be relatively fast or relatively slow. Deformation can be a smooth continuous process or it can be a series of abrupt direct discontinuous movements. It is also of interest how far the piston is pushed back by the sample after the pressure is released from the air piston, which is how much the sample recovers. The collection of this data during the tightening process will allow the calculation of several parameters vital to a successful tracking work, including Poisson's Ratio and Young's modulus.
[071] Analysis of these parameters using the state of the art in the industry usually requires expensive acquisition of a conventional core, or rotating sidewall cores, followed by expensive and time-consuming measurements in a laboratory usually at a significant distance from the well . It is often months after the well is drilled before the results of these measurements are known.
[072] The fracturing of oil drilling cuts can be quickly determined either in the laboratory or at the well site. The lead time for transporting the samples to the laboratory
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36/164 followed by the analyzes can be less than 24 hours. This is fast enough for the data to be used in deciding the final way in which the well will be completed, such as which zones will be drilled or where a horizontal side will be seated after drilling a vertical pilot hole.
[073] Even faster results can be obtained by measuring the fracture of the well site at the same time as the well is being drilled. This can be done by manually collecting the samples and then loading an instrument at the well site for analysis. In another aspect of the invention, fracturability can be determined at the well site using an automated instrument that takes a sample of drill cuts and tightens them and monitors deformation. Such an automated device would not require loading the cut samples into a container. The cuts can fill a deformable compartment in the well-site fracture apparatus. After filling the said component with the cuts, the device's clamping mechanism tightens the cuts at the same time that the amount and the systematic deformation of the sample deformation are recorded using a linear translation or another type of measurement meter. The data thus collected would then be stored on a computer and can be instantly integrated with other drilling parameters generated by other instruments in the well, including profiling tools during drilling, such as gamma ray profiling during drilling, penetration rate , drill weight, mud profile displays, etc.
[074] Real-time fracture data can be combined with other real-time data to determine the ideal medium for drilling the well. The data can be used to help conduct horizontal lateral wells to remain in the ideal formation.
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37/164 [075] In one aspect, the invention provides a method for analyzing the fracturability (ductility or hardness) of a material, such as a geological formation, which comprises the steps of (a) providing one or more analyzable samples of the material , (b) subjecting the sample to one or more forces that are capable of compressing the material of a particular hardness or ductility and (c) determining the amount of compression of the sample caused by one or more forces. The analyzable sample will typically, but not necessarily, be from or associated with an oil well or oil exploration. The most basic form of the fracture method is distinct from the previous approaches used to assess the hardness of a geological material, which either depend on scratching (for example, the classic Mohs scale test) or penetration of a point on the material or point contact with a material surface (such as with the use of the Schmidt rebound hammer), although such methods can be combined with the basic fracture method. In one aspect, the compressive force is applied to at least one entire side of the sample. More typically, the compression force will be applied to multiple sides of the sample contemporaneously (within 2 minutes, within 1 minute, within 10 seconds, within 5 seconds, within 3 seconds or within 1 second of each other) and , more frequently, simultaneously. Often, the compression force (or forces) will be applied isotopically, that is, it will be applied to all sides of the contemporary sample or simultaneously. When advantageously combined with other methods of the invention, the compression study will be conducted in a compressible container, as exemplified elsewhere in this document. The sample is often a cut or take from a core sample associated with an oil well or oil exploration. So in many ways, the size of the
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38/164 sample will be the size of a cut, as explained elsewhere in this document. In one aspect, the method is performed on cuts that are associated with oil-associated mud. In other respects, the method involves washing the sample before crushing.
[076] An additional distinction in the typical application of the method of fracturing method and methods for assessing the hardness of geological materials in the prior art is that the method of fracturing, especially when applied to cuts, is applied to a large number of materials (at least 10, typically at least 20 and often more, such as at least 25, at least 30, at least 40, at least 50 or more) that are obtained from different depths and / or different locations within a relative depth zone , and often such materials are brought to the surface within the relatively short amount of time that is required for oil drilling (for example, about 1 day to about 12 months, such as about 1 to 300 days, about 1 to 250 days, about 1 to 240 days, about 1 to 200 days, about 1 to 180 days), so that the samples comprise several samples obtained during this period (for example, a major that of the samples is obtained within 200 days of each other or at least 20, at least 30, at least 35, at least 40, at least 50 or more of the samples in the analysis are obtained within at least 240, at least at least 180, at least 120, at least 90 or at least 60 days apart). Currently, assessments to track suitability have typically been made using (1) mineralogy assessments, which determine the mineral structures present in the drilling area or potential drilling area through sampling, (2) X-ray diffraction methods to similarly assess the content geological area (within the limits of detection of this method) and (3) assessment of the
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39/164 total organic area exposed to the material. These practices can be combined with the compression fracture methods provided by this invention, in certain aspects, to provide additional information about the material. However, in another aspect, the compression fracture can be performed as an evaluation method without using any of these methods.
[077] A collection of samples assessed for fracturability, such as cuts, may consist entirely of samples obtained from locations in the material that are at least about 0.15 meter (0.5 foot) apart and typically (but not necessarily), up to about 30.48 meters (100 feet) apart from each other (for example, they can be from well depths that are at least 0.15 meters (0.5 feet) apart, at least at least 0.23 meter (0.75 feet) away, at least 0.3 meters (1 foot) away or even more distant, such as at least 0.43 meters (18 inches) away or at least 0 , 61 meter (24 inches) away), or the sample set may consist substantially of (for example, at least 85%, at least 90%, at least 95%, at least 97%, or at least 99%) samples obtained from locations characterized by such differences, or the sample set may be characterized by the fact that a majority of the samples were obtained going from locations that have differences in space, or at least a large proportion (such as at least about 10%, at least about 20%, at least about 25%, at least about 33%) of the samples was obtained of locations that have such relative spatial separation. In view of the possibility of lateral drilling, the separation between the samples could, also or alternatively, be in the same zone of relative depth (for example, within the same vertical zone of 152.4 m, 121.92 m, 106.68 m , 91.44 m, 76.2 m, 60.96 m, 45.72 m, 30.48 m, 15.24 m, 9.14 m or 7.62 m (500 feet, 400 feet, 350 feet, 300 feet, 250 feet, 200 feet, 150 feet,
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40/164
100 feet, 50 feet, 30 feet or 25 feet)). In some respects, multiple samples from approximately the same site are tested, but the pool comprises several samples from different sites (for example, at least 10, at least 20, at least 30, at least 50, at least 100, at least 150, at least 200, at least 250, at least 300, at least 400, at least 500, at least 750, at least 1,000 or more samples, from locations in the material that are at least about 22.86 centimeters (0.75 feet) ) away from each other). The number of total samples used in such a method will typically be greater than about 10, such as greater than about 20 and can often be significantly more samples, such as at least 50, at least 100, and can be in the range of 10 to 5,000, 10 to 3,000, 10 to 2,500, 15 to 3,000, 15 to 2,500, 20 to 3,000, 20 to 2,500, 25 to 3,000, 25 to 2,5000, 25 to 2,000, 20 to 2,000, 10 to 2,000, 20 to 1,500 , 25 to 1,500 or 10 to 1,500 samples. The total assessment area can be significant, such as at least about 0.4 kilometers, 0.53 kilometers, 0.8 kilometers, 1.21 kilometers, 1.61 kilometers, 2.01 kilometers, 2.41 kilometers, 2.82 kilometers, 3.22 kilometers (0.25 miles, 0.33 miles, 0.5 miles, 0.75 miles, 1 mile, 1.25 miles, 1.5 miles, 1.75 miles, 2 miles ) or more in depth and / or horizontal area, reflecting lengths of modern oil wells. Thus, the fracture methods of the invention can provide a relatively quick map of the fracture suitability of a well site. In some respects, the entire analysis is conducted close to the well site (such as within 60.96 meters (200 feet) from the well site). This can be achieved with the use of the devices of the invention that compress material close to the point of separation of the cuts and sludge, for example, in oil drilling.
[078] In some respects, the compression fracture methods of the invention are combined with other methods
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41/164 described in this document to assess the hydrocarbon content of a material through the release of volatile compounds, such as organic acids, that can be released using the methods described in this document (for example, applying a soft vacuum, trapping and, optionally, analysis by sensitive methods, such as analysis by mass spectrometry). In other respects, the invention's fracture methods and the volatile compound analysis methods of the invention are practiced separately. Similarly, for the devices of this invention, such devices may comprise components / systems of combined volatile and fracturability analysis, but the invention also provides devices that understand these functions as individual resources.
[079] Some aspects of the invention, particularly those in which the volatile compound analysis will be carried out as a part of the inventive method, are characterized by comprising a step in which the sample material is quickly stored, and typically in a sealed manner, after reach the surface or otherwise be exposed to normal atmospheric conditions. For example, at an oil well site, such a method may comprise collecting cuts in a sealed container within a short amount of time after such cuts reach the surface. The time for collection can vary with the nature of the sample, the method to be applied and the target material (or target materials) that is sought to be identified by the method. In an exemplary aspect of the invention, the samples are sealed in a sealable container in about 5 minutes or less, but, more typically, the time will be about 3 minutes or less, about 2.5 minutes or less, about 2 minutes or less, or even about 1.5 minutes or less, such as about 1 minute or less. Samples can be washed immediately before
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42/164 seal in a sealable sample container. Sample washing can be performed by any suitable method. More generally, but not necessarily, cuts or other materials are typically stored so that the volatile compounds contained therein are not lost below limits detectable by the method. Gases and volatile chemicals that expand rapidly under atmospheric pressure and unrestricted conditions, such as petroleum-related hydrocarbons, can be readily released from such materials once they reach the surface. Consequently, it is advantageous to store materials to be analyzed, such as cuts, inside one or more containers that will guarantee no release or little release of such substances during the time that the material must be stored and / or transported. In a preferred aspect, the materials are stored in one of the devices described elsewhere in this document, and, with maximum difference, that device is configured to fit tightly within one of the analytical devices of the invention described elsewhere in this document, such as engaging an inlet or using a flow channel device, such as one of the needle devices discussed herein.
[080] A filter material can also be added to the sample container. Any type of suitable filter material can be used. Suitability in this regard generally means that substantially all (for example, at least about 95%, such as at least about 99%, or at least about 99.9%) the material (excluding volatiles released from the material ) is kept inside the sample container and does not enter or make contact with the inlet or flow channel. Simple filtering materials, such as cloth materials and cotton pellets, have been shown to be suitable for this purpose. These materials, as with other materials used
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43/164 in the sample container and throughout the system, must be inert in relation to the reaction with volatile chemicals and emission of materials that would interfere with the analytical aspects of the inventive methods. [081] In one aspect of the invention, the sample (or samples) that is analyzed in the method is or comprises a drilling mud. Sludge has been discussed elsewhere in this document. The mud can be an oil-based mud or a water-based mud. Sludge analysis typically means that more than one sample of sludge is taken. This is due to the fact that the material can be kept in a mud over several mud reuses (or mud passes to the drill bit point and the surface on which a sample can be taken). Consequently, samples can be taken at points that correspond to a “rising mud (mud that reaches the surface) and a“ falling mud that returns to the well, which will help to identify changes in the mud over time, assisting in the analysis. of the material by studying the mud. In one aspect, the method comprises the analysis of mud and cut materials. In yet another aspect, the method comprises the analysis of mud materials, cuts and / or fragments of core samples, such as samples from each of these categories taken from an oil well or oil exploration site.
[082] The material and the sample are typically a solid (as in the case of a cut), but in other aspects of the invention, the sample and / or the material is a liquid or a gas, and in still other aspects, the sample and / or material is a mixture of two or more from a solid, liquid or gas or a combination of all three forms of material. For example, in an industrial environment, samples can be taken from the air to ensure that the amount (or quantities) of certain compounds (for example, benzene) is within certain levels. In yet another modality, the method is applied
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44/164 to search for leakage, such as leakage of gases into and / or out of a geological formation. Geothermal activity can also be assessed by the method. In another aspect, the method can be practiced with a liquid, such as water, to assess the level of certain substances in the liquid (such as contaminants in water samples). As noted elsewhere, the material can be of natural, synthetic or semi-synthetic origin and can be generated from a variety of origins and / or configurations, such as industrial solids, soft materials, liquids and air or other gases.
[083] In preferential aspects, the method is applied to analyze the volatile compound content of the material. Volatile products in rocks typically contain important information used for exploration and production of oil, geothermal and mineral energy. Volatile products in rocks can also be used to determine the suitability of carved stone for road and building construction. Volatile products in rocks and soils can also provide information beneficial to ecological and environmental studies. Volatile products in solids that form as a by-product of various industrial or civil processes, such as scales that can form in the coating of oil, gas and water wells, can provide information that can help to design processes to inhibit the formation of such unwanted solids. Volatile products in artificial solids, such as bricks, concrete, ceramics, glass and plastics, can be used to check problems in their manufacturing process or to assess their usefulness for various applications. Volatile products that occur in solids that form in natural biological systems, such as bone, teeth, kidney stones, fingernails and toenails, can provide insights that could help maintain or improve the health of the individual or community from which these solids originate. The products
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45/164 volatiles in softer tissues of plants and animals, including humans, may also offer diagnostic information that may be useful for the health of the source organism. Such methods may have application in tests of food safety, food viability, food storage and / or conservation or similar. Volatile products in industrial and natural liquids also contain a wealth of information that can impact the success and profitability of oil, thermal energy and mineral exploration and production; the efficiency and profitability of manufacturing and other industrial processes; and the health and well-being of the environment, organisms and communities. Various explosive products can also have distinct volatile signatures that could be detected with the device described in this document, so volatile air or solids monitoring can be beneficial in keeping people, communities, military and police safe.
[084] In one aspect of the invention, the sample is taken from an outcrop and the material comprises an outcrop. Outcrops are geologically important formations. In one aspect, outcrops are used as a comparator to underground materials, such as materials obtained from a mine or drilling site. Such materials may also contain evidence of materials leaking to the surface.
[085] The material is typically dry, but in some aspects of the invention it is damp or even wet (for example, in the case of a liquid or a mud). In some aspects of the invention, it may be important to ensure that the amount of a liquid, such as water, in the material, is not so high as to exceed the capacity of the mass spectrometry device. However, in general, this is not a limiting factor, and the person skilled in the art will have the ability to assess if any such situation arises. As already noted in the present
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46/164 document, the material, and thus the sample, will typically contain one or more volatile substances that release passively or will be released by applying one or more forces to the sample. In either case, a gas will be released from the sample that contains one or more volatile substances, although, as discussed elsewhere in this document, the sample may also contain non-volatile substances, which can also, or alternatively, be collected and considered as part of the analytical aspect of the inventive method. The nature of the volatile substances contained in the sample can vary considerably, and inventive methods can be practiced with various types of volatile compounds. In specific aspects, however, the sample and material contain a significant amount of one or more specific target substances. For example, in the case of drilling cuts taken from oil production at exploration sites, the sample will contain detectable amounts of one or more species of C1-C20 hydrocarbons and related compounds that contain oxygen, nitrogen, sulfur or other heteroatoms; organic acids (for example, C1-C5 organic acids, particularly, C1-C3 organic acids and, more commonly, acetic acid, carbonic acid and / or formic acid); and / or one or more inorganic gases, such as hydrogen, helium, carbon dioxide, carbon monoxide, water, nitrogen, argon, oxygen, hydrogen sulfide, carbonyl sulfide, carbon disulfide and / or sulfur dioxide. In one embodiment, the sample comprises C1-C15 hydrocarbons, such as C1-C14 or C1-C12 hydrocarbons, and the method comprises analyzing one or more of such hydrocarbons. In yet another aspect, the sample comprises C1-10 hydrocarbons, and the method comprises analyzing one or more of such hydrocarbons. In aspects that are often preferred, the invention is also, or alternatively, characterized by the detection of acetic acid,
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47/164 carbonic and / or formic acid contained in the sample or formed from the application of one or more sample forces in the practice of the inventive method. In this regard, the sample can be characterized as comprising one or more compounds that form such compounds or having material that can form carbon dioxide, carbon monoxide, methane and / or water.
[086] In another facet, the inventive methods provided in this document can be characterized by the fact that such method comprises conducting a sample analysis for one or more substances containing a carbon chain of five or more, such as six or more, or seven or more carbon atoms. In some cases, the method comprises heating the sample or gases to assist with the analysis of longer-chain hydrocarbons or other compounds that comprise carbon chains, such as hydrocarbons that have a backbone of more than 10 carbon atoms. For example, the method may comprise heating the sample or gas (or the device containing each or both) to about 130 Ό or more, about 140 Ό or more or about 150 Ό or more, to assist with the analysis of such longer chain hydrocarbons. In this and other aspects, the method may comprise controlling the temperature during which some or all of the process is carried out, such as the temperature at which gases are released and / or analyzed by the method's analytical processes. Such methods can typically comprise heating the entire inlet system, through entrapment, to the mass spectrometer and through the outlet. In other respects, it is preferable that the method is generally carried out at room temperature, although, in such respects, it may also comprise using freezing as a means to trap volatile products and / or applying heat to release the compounds from a mechanism or medium. of imprisonment for
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48/164 freezing.
[087] In some respects, the invention is characterized by not creating new volatile compounds in the sample, such as forming volatile products from hydrated minerals (where water is a part of the crystal structure, such as silicate clay minerals; hydrated oxides, such as brucite (MgOH2) and goethite (FeOOH); and other mineral substances containing water, such as hydroxyapatite; etc.) or in which, for example, carbon dioxide is part of the crystal structure (such as calcite ( CaCOs), dolomite (CaMg (CO3) 2) and siderite (FeCOs)); and solid and liquid non-volatile hydrocarbons as a gas under analytical conditions under which the methods of the invention are performed, such as C20 alkanes or various bitumines or kerogens; or any other substance that is not normally a gas or normally emits a gas under such conditions.
[088] In practicing the methods of the invention, one or more gases are typically released or extracted from the material sample. In some contexts, the gas can be released passively (without applying force or without applying significant force); for example, exposing the sample or the container comprising the sample to a release channel or release passage, such as a needle or similar device that penetrates the container containing the sample. In other contexts, as noted elsewhere in this document, the methods may, also or alternatively, comprise applying energy to the sample, such as by mechanical force, for example, crushing the sample or crushing a container that has a crushable portion and which contains a crushable sample. In each case, the gas or gases are released from the material sample and are then allowed to flow so that one of the additional steps of the method can be performed on such a gas. The amount of time required for the gas to be released may vary with the conditions of the
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49/164 method, including material, whether forces are applied to the sample or not, the time that the gases are allowed to be released from the sample and the sensitivity of the analytical methods performed on the gases. Using the guidance provided in this document, those skilled in the art will be able to determine these conditions. For samples that are analyzed at atmospheric pressure without applying force, a time of about 1 second may be sufficient, for example. Longer or shorter periods may be suitable, but such a relatively short period may be desirable. Longer periods can cause the sample to be under lower pressure conditions because of the relatively lower pressure condition of the device.
[089] In many aspects of the invention, volatile substances are extracted from a sample by subjecting the sample to various vacuum levels. For some samples, additional important information is obtained by subjecting the sample to an increasingly lower pressure range, in other words, to an increasingly higher vacuum level, and by analyzing the chemistry of each individual aliquot extracted at each pressure of individual extraction. This proved to be especially useful for solids, particularly for various rock samples including outcrop, core and cut samples as applied to oil and gas exploration and production. Depending on the sample and the problem being solved, several other processes can be applied to the sample before any vacuum extraction, between the vacuum extraction steps, or even during a vacuum extraction step, as will be discussed further in the present document. In one example, another process that can be applied, and which is described elsewhere in this document, is to crush or squeeze the sample or to apply any process that mechanically breaks the solid sample. Other processes that can break
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50/164 the sample includes sawdust, or drumming, or exposure to vibrational energy at any number of frequencies. Another process that could be employed is to heat the sample; an effect of which may be the rupture of the sample by thermal decrepitation of fluid inclusions and / or other structures in the sample. Chemical processes and / or application of energy can also or alternatively be applied to the sample in the performance of the method, such as, for example, applying an acid to the sample in order to dissolve certain substances. It is also possible that, in some cases, a combination of two or more of these or other disruption processes can be usefully applied to the practice of inventive methods.
[090] The method may also include one or more steps taken before the release of gases or between the release of gases (in methods where there are multiple release steps or multiple samples analyzed). In one aspect, the method comprises purging some amount of air from the sample, for example, by applying a vacuum. In such embodiments, the time during which the vacuum purging is applied will generally be such that the quantity (or quantities) of volatile products that are purged with air is small enough to justify the purging step. This can comprise, for example, applying just 1 or 2 seconds of vacuum pressure, in order to reduce the pressure from about 1,000 millibar to about 50 millibar (but these are only exemplary figures). However, such a purging step can be important when the presence of air as a contaminant will interfere with the analysis. This can be important in relation to the analysis of older samples contained in open environments.
[091] In a further specific aspect, inventive methods may comprise purging the sample, which may be a sealed sample and replacing the purged air with another gas, such as argon,
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51/164 nitrogen or helium or any other suitable gas as determined by the specific advantage obtained for the specific problem being solved and the specific host solid and specific volatiles being analyzed, argon is typically preferred in that nitrogen and helium may be relevant in sample analysis.
[092] These steps of purging (and optionally replacing) air or other surrounding gas provide a means of removing potentially interfering substances in the air or other gas in which the sample is contained that may provide false signals in the analysis (for example, confuse methane with oxygen or nitrogen species found in the air). Other methods of achieving the same goal may be available in the art and equally suitable, but this method is preferred in many aspects of the invention. For example, in an alternative, the air or gas in an internal sample container is displaced with a liquid, such as a diffusion pump oil, and the internal sample container is placed in a surrounding external container. The internal sample container comprises or is typically made entirely of a material that can be crushed or compressed by applying force. A vacuum is applied to remove any air from the surrounding container, creating a vacuum condition in the space formed by the surrounding container, and the entire sample container sealed. A force that compresses or crushes the sample in the inner container is applied, breaking the inner container and releasing the volatile products into the now exposed outer container. Such materials can then be subjected to further analysis in accordance with the methods of the invention described in this document with little risk of interference of substances in the air, etc.
[093] Rapid purging of sample air and rapid replacement with argon or other gas before crushing the sample can be
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52/164 particularly relevant in the analysis of samples relevant for oil and / or gas exploration. Generally, these methods are applied to older samples kept under open conditions, as there is an exchange in terms of loss of volatile substances in the application of purging methods. Thus, for sealed samples, such methods may not be practiced.
[094] Purge (and purge and replacement processes) can facilitate mass spectrometer analysis of very small quantities of certain substances, such as methane, using mass 15 for the CH ₃ ⁺ ion, removing nitrogen and oxygen. The lower resolution of many quadripolar mass spectrometers makes it difficult to analyze trace methane with the use of mass 15 in the presence of larger amounts of nitrogen with a larger peak in mass 14 and oxygen with a larger peak in mass 16. Purging and replacement of air by other gases can have other benefits. Replacing air with krypton, which has a mass of 86, would solve the problem of interference from methane as well as argon, but it could also assist in the extraction of some volatile recalcitrant products in the solid, giving a much greater amount of energy in the collision with the lighter gases. present as the empty spaces in the sample are evacuated.
[095] Most purging steps are completed quickly, especially when the step comprises removing air from the system by means of a rapid vacuum (versus inert gas flow or a combination of both types of steps). For example, in one aspect, the purging process is completed in about 10 seconds or less, such as about 5 seconds or less, about 3 seconds or less, or even about 2 seconds or less. In the case of a quick vacuum purge, the application of such a step for less than about 3 seconds, such as less than about 2 seconds,
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53/164 less than about 1.5 seconds, or even 1 second or less can be advantageous. Another way of characterizing this step in some respects is that the vacuum purging step results in a loss of less than about 5%, less than about 2%, less than about 1%, or even less losses ( for example, less than about 0.5%) of oil and, for gases, losses are less than about 10%, less than about 7.5%, less than about 5% , less than about 3%, or less than about 1% of the gas present at the time the sample is introduced into the system. Purge is typically carried out before crushing or squeezing materials or applying other forces to the sample. At the well site, samples may not be purged as almost all information can be converted to data, especially using control sampling devices / systems that are used to calibrate the system (in relation to gases in the site and are not associated with the samples). For sealed samples, the method may also not be purged, as this may result in data loss. As such, purging steps are often optional, but can be useful when there is a determination that there could be a risk of an interference signal.
[096] Depending on the problem being solved by the analytical method, it may also be, or alternatively, advantageous to heat or cool the sample before volatile extraction. The heating or cooling of the sample can be carried out alone or with crushing and / or purging (or purging and replacing the air or other surrounding gas). For example, if volatile products in water ice are to be analyzed, the sample would need to be held at a temperature cool enough to keep the ice frozen during volatile extraction and any purging and exchange of gas for air preceding crushing. A temperature of minus 50 degrees Celsius can be
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54/164 needed in this example to keep the sublimation ice in response to the applied vacuum. A similar process could be advantageous in the analysis of gas hydrates, otherwise known as clathrates.
[097] Centrifugation can also, or alternatively, sometimes be an aid to volatile extraction. Centrifuging a vertical sample before volatile extraction, for example, can cause the vertical stratification of volatile products in the container, the gases would migrate to the top, and the oil would, in general, form a layer on top of the water. This can be particularly useful in the analysis of volatile products in drilling muds from oil and gas production and exploration wells. Centrifugation after crushing can sometimes also have similar advantageous effects.
[098] After all preparatory processes, if any, are completed, volatiles are typically extracted from the sample by reducing the pressure in the sample by exposing the sample container to an inlet system that is under static vacuum and is not being actively pumped. The inlet system is typically sealed to vacuum pumps at this point in the process, having previously been evacuated by vacuum pumps. Pressure in the sample is reduced by opening a valve between the sample container and the inlet system allowing gas to pass from the sample through the needle or other flow channel device to the inlet system. During a multistage extraction, at increasing vacuum levels for each extraction, the first extraction results in a resulting pressure in the sample and inlet system that is determined by the pressure of gas in the sample and the sample container, by the volume of space sample container and the volume of the static inlet system. Each collection of extracted gas (or gases) obtained by such a method is called an “aliquot in this document. So, for example,
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55/164 the first extraction of a gas at atmospheric pressure or at a different pressure can be called aliquot 1, with subsequent aliquot numbers, each increasing by one, so that a three-stage analysis has aliquot 1, aliquot 2 and aliquot 3. In typical practice, aliquot 1 is extracted at a pressure of about 50 millibar. A typical aliquot 2 is extracted at an initial pressure of about 5 millibar, and this pressure for a typical aliquot 2 is decreased by an active pumping period after the initial trapping of the most volatile gases at about 0.001 millibar or less (for example , as low as 0.0001 millibar or less, or any range between about 0.001 millibar and 0.0001 millibar, such as 0.005 to 0.0005, 0.00075 to 0.00025 or 0.0009 to 0.0002 millibar) . The step to cause this significant type of pressure drop in the system, device or method of the invention is advantageous in the methods in which a mass spectrometry analysis is performed on the samples, as the mass spectrometry conditions typically require higher pressures lower than those in which aliquot extraction methods are performed in order to operate properly. Such pressure conditions will be known in the art (or provided by the manufacturer of mass spectrometry) and the achievement of such pressure levels can be achieved through any suitable means, with many such methods and devices being available.
[099] As mentioned elsewhere, the methods of the invention may, in certain cases, include one or more steps in which potentially interfering gases are removed from the released gas or from the environment in which the gas is released. For example, in one aspect, the invention may include the step of flooding the device in which the method is carried out with an inert gas, such as argon, in order to remove gases from the device, which may provide false signals or results. Normal atmospheric gases, such as oxygen, nitrogen and / or
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56/164 both, for example, can be substantially removed, or almost completely removed, or even entirely removed (at detectable levels) by administering (“flooding”) the device or a portion of the device on which the method is performed such gas inert. Such a method can also be used as a method to renew the device between samples. When an inert gas is used in such aspects, the inert gas can be any suitable gas that does not react chemically with the sample and does not cause any interference with the chemical analysis of the sample's volatile products. In other respects, a non-gaseous material, such as a liquid, can be similarly used. Atmospheric gas or other interfering gas can be purged from the device, component or environment in which the sample is being analyzed, for example, by rapid vacuum extraction (for example, applying a vacuum that is strong enough to remove substantially or almost entirely the purge inert gas for a duration of about 1 second or less). In another aspect, the method may comprise an inert gas flowing through the sample container or area to displace the potentially interfering gas. Such methods are not included in every application of the inventive methods. For example, when the method is performed on samples sealed at a collection site, such as a well site, such a step is typically not performed. However, such purging steps can be useful for analyzing the presence of target substances in which such substances are or are suspected to be present only in very small quantities, such as in relation to methane and / or helium in samples that are associated with oil production and exploration sites.
[100] Materials or methods can also or alternatively be used to remove other potentially referring substances, such as water vapor, for example, which is relevant to certain aspects of the invention in which water is formed and analyzed as a
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57/164 method for analyzing the hydrocarbon content in the samples. In one aspect, the invention is carried out in the presence of a material that can capture essentially all, substantially all or a relevant portion of the water vapor present around the sample that can be captured by trapping or by other tools to capture substances used in the analytical method. For example, the system that is used to perform the method may comprise passages between system elements that are made of stainless steel, which promotes water absorption and thus removes water vapor contained in the gas content flowing through the system to reach the next stage of the system.
[101] The quantity of volatile substances released from the sample, trapped in the trap or analyzed by the analytical method of the inventive methods described in this document can constitute any suitable proportion of the volatile products present in the sample, and the quantity contained at each such stage in each one. of the aliquots contained in the multi-aliquot methods of the invention can also be any suitable amounts. Typically, most volatile products are captured by the method, so that at least about 90%, at least about 95%, at least about 97%, at least about 99% of volatiles (excluding water, and particularly in relation to C1-C10 hydrocarbons and similarly structured organic compounds) are extracted from the sample, by practicing the methods of the invention. The efficiency of the system is typically also high in relation to the trapping of gases that are condensable in trapping. Typically, condensable gases that can be captured by trapping are not trapped in the system at detectable levels. However, as discussed elsewhere in this document, certain gases will not condense on entrapment or otherwise be trapped
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58/164 by imprisonment and must be subjected to manipulation by other means to be captured and analyzed by the method.
[102] To exemplify (and clarify), the methods of the invention may comprise the analysis of a single aliquot, for example, a single aliquot obtained under conditions of mild / low vacuum, or, in other respects, the method may comprise obtaining and analyze a plurality of aliquots of one or more samples and / or that are obtained under different conditions. For example, one method comprises obtaining two aliquots per sample, where the first aliquot is obtained by applying about 50 millibar (for example, 10 to 100 millibar, such as 15 to 95 millibar, 20 to 90 millibar, 30 to 80 millibar millibar or 40 to 70 millibar) for about 3 minutes (for example, 1 to 10 minutes, such as 1.5 to 8 minutes, 2 to 7.5 minutes, 2.5 to 5 minutes or similar, in some cases, it may be advantageous to perform the first aliquot extraction for shorter times in this or other contexts, such as 0.25 to 4 minutes, 0.33 to 3.5 minutes, 0.5 to 3 minutes, 0.5 to 4 minutes , 0.5 to 5 minutes, 0.5 to 2.5 minutes, 0.5 to 2 minutes, 0.75 to 3 minutes, 0.75 to 2.5 minutes, 0.75 to 2 minutes or other interval time) and obtain a second rate by placing the sample under pressure conditions of about 5 millibar (for example, about 1 to 10 millibar, about 2 to 8 millibar, about 3 to 7 millibar or similar) by a period of about 10 minutes (such as 5 to 15 minutes, for example, 6 to 12 minutes, 6 to 10 minutes, 5 to 9 minutes, 6 to 9 minutes, 7 to 9 minutes, 7 to 10 minutes or about 7 minutes, about 8 minutes or about 9 minutes ), with the method optionally including a step of crushing / squeezing the sample during one or both aliquots, such as crushing the sample at the beginning of the first aliquot extraction, as described elsewhere in this document. In some respects, shorter extraction times (for example, less than about 5 minutes, less than about 4.5 minutes, less than about 4 minutes
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59/164 minutes, less than about 3 minutes, less than about 2.5 minutes, less than about 2 minutes, less than about 1.5 minutes, less than about 1 minute, or even shorter periods. In such aspects, the system and method parameters can be adjusted to facilitate a shorter extraction time, such as, for example, using a needle system of relatively larger diameter for the passage of volatile products out of a container of perforated sample (for example, using a needle of about 3.18 or about 1.59 millimeter (1/8 or about 1/16 of an inch) inside diameter compared to a needle of about 0, 79 millimeter (1/32 of an inch) in diameter). In another approach, the extraction time and / or purge time can be reduced by passing a non-condensable purge gas through the sample.
[103] In some contexts, it may be useful for the method of the invention to be carried out and / or the device of the invention to be provided with a plurality of trapping devices, which can be of the same or different nature. Thus, for example, in one aspect, the invention includes a plurality of non-selective entrapments, such as a plurality of liquid nitrogen entrapments. This type of system device can be particularly advantageous with multiple aliquot methods. In such methods, it may be possible that each rate or at least a subset of the total number of rates is associated with each lockup. This can, among other things, speed up the process of performing multiple rate analyzes, for example, by exposing the rates to the prisoners separately or by operating the prisoners at different times, and so that there is little downtime in the system in the event that a prisoner needs to be clean, configured or reconfigured between uses. When entrapments with different properties
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60/164 functionalities are provided, using different entrapments can improve the information obtained from the method, providing different dimensions for analysis (for example, combining one or more non-selective entrapments with one or more selective entrapments, such as GC entrapments) .
[104] As already noted, the gases released from the sample are released to a system or device in which the remaining steps of the method are performed. Typically, gases pass to the system or device through an inlet, which can be a portion of the system or devices associated with a needle or flow channel as discussed elsewhere in this document or can be any other suitable type of inlet. Thus, the processes employed before and during the vacuum extraction may include attaching the sample container to the inlet system before the vacuum extraction starts and any auxiliary processes. Various processes can be used to secure the sample container to the inlet system. They are described in the section on the various possible configurations of the sample container. The preferred sample container is a sealed brass tube with a tightly sealed nitrile cap on the top and a neoprene plug on the bottom. Using the typically preferred sample container, the sample container is attached to the inlet system before the vacuum extraction starts by passing a needle through the nitrile cap. Other types of sample containers must be sealed by other means appropriate to the inlet system before vacuum extraction begins.
[105] Another step in the inventive methods may, also or alternatively, include applying energy to the gases generated in the practice of the inventive methods, which may include gases directly released from the sample or gases that are released from the device or trapping device of the invention (the “ imprisonment, as
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61/164 further described elsewhere in this document). The amount of energy and the type of energy applied to gases in such aspects can be in any quantity and form suitable to generate one or more other target substances which, for example, are more convenient for the detection and / or analysis of the than the substances that were in the gases before the energy was applied. For example, the methods of the invention may comprise a step of applying a source of energy, such as a source of light energy to a gas, thus forming compounds from organic acids, such as carbon monoxide, water, dioxide carbon, methane and the like, in quantities that are suitable for detection by the analytical aspects of the inventive methods. Carbon monoxide is often preferred as a detection molecule in which it typically has no signs of potential competition which can sometimes present problems in analyzing water or carbon dioxide. Carbon monoxide is generated by the breakdown of formic acid (HCOOH) to water (H2O) and carbon monoxide (CO). This reaction occurs even at pressures of about 1 atmosphere, so much so that some large bottles of formic acid are provided with a vent that allows the carbon monoxide to escape and thus avoid the accumulation of unwanted pressure in the bottle. In contrast, acetic acid (CH3COOH) breaks down to water (H2O) plus methane (CH4), and carbonic acid (H2CO3) breaks down to water (H2O) plus carbon dioxide (CO2). Carbonic acid is only stable in solution and has no gas phase.
[106] The amounts of organic acids released from materials, such as cuts, can be very small, and their respective indicator breaking compounds can be masked by larger amounts of these compounds being released as compounds existing as those compounds in the sample. In
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62/164 geological samples, this is especially true for water, carbon dioxide and methane. This is not a usual problem for carbon monoxide as its natural occurrence in oil and gas well samples is minimal at best. However, carbon monoxide can be generated as a by-product of oil and gas drilling by the process known as drill burning ^- or drill bit metamorphism '. In an aspect of the laboratory apparatus of the invention, and related methods of use, some of the compounds derived from organic acids which are also present as naturally occurring interfering compounds, such as water and carbon dioxide, are frozen to a trap of liquid nitrogen ( LN2). Carbon monoxide and methane do not freeze when trapping LN2. However, methane as a naturally occurring substance is common in rocks from oil and gas wells. Therefore, the presence and amount of methane in the rocks of oil and gas wells is not an adequate indicator of precursor organic acids. Carbon monoxide is not common as a natural component of oil and gas well rocks. Therefore, the presence of carbon monoxide is typically a good indicator of organic acids. Thus, for example, in a number of ways, the methods of the invention comprise detection of carbon monoxide, but not methane or at least do not comprise methane levels related to general levels of organic acids in the material associated with the sample / cuts.
[107] In certain respects, carbon monoxide is monitored using the AMU12 fragment used by carbon monoxide mass spectrometry analysis. In a more particular aspect, the method comprises carrying out a method in which carbon monoxide is a primary indicator of organic acids in the material and is analyzed by evaluating the presence and quantity of the formed AMU12 fragment
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63/164 by mass spectrometry performed on carbon monoxide, and the method is performed without any detectable amount of carbon dioxide or in the presence of an amount of carbon monoxide that does not result in a distortion of the AMU12 signal associated with carbon monoxide carbon or the degree of the AMU12 signal that is associated with carbon monoxide. In some respects, the amount of interference with AMU 12 signal from the presence of carbon dioxide in such a method is less than 25%, less than 20%, less than 15%, less than 10%, less than 5%, less than 2% or less than 1%. In environments where carbon dioxide is present, the method may comprise manually or automatically correcting the AMU12 signal data for the presence of carbon dioxide to obtain an AMU12 signal associated with carbon monoxide. In some respects, the step of isolating carbon dioxide is handled using a trap that collects carbon dioxide, such as a trap of liquid nitrogen, in a way that carbon monoxide and carbon dioxide are not associated rates ( for example, carbon monoxide in a laboratory device of the invention can be collected in a state of non-condensable gas, while carbon dioxide is attached to the trapping of liquid nitrogen). In other respects, the method for analyzing the level of carbon monoxide also or alternatively comprises analyzing the signal of AMU13 and / or AMU 16 and / or 28. In aspects where carbon dioxide is initially present, but removed or substantially removed ( for example, by removing at least 85%, at least 90%, at least 95%, at least 97%, at least 99% or more of the initial concentration) as part of the method of the invention, a CO2 absorber, such as DecarbiteTM can also or alternatively be used to reduce or eliminate any detectable levels of carbon monoxide in the gas or aliquot to be
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64/164 analyzed, also or alternatively, a mass spectrometer-based machine designed to detect residual amounts of carbon monoxide in cuts can be designed to use any of the CO2 elimination / reduction techniques described in this document and its equivalents known in the art.
[108] In another aspect, the method is carried out under conditions in which the application of energy also or alternatively changes the pressure of gas associated with the sample or generated from the sample in a manner or quantity that is indicative of a chemical change that identifies the presence of a target substance or a substance related to the target (such as carbon monoxide).
[109] It is important to note that, although in many aspects of the methods of the invention, mass spectrometry analysis is an important component of the method of the invention, such a step is not always included (and is often not included) in these methods. Instead, other analytical steps can be taken to identify the presence of the target substance or target-related substance. For example, a carbon monoxide meter or measuring device can be used to directly measure the formation of carbon monoxide in a petroleum-related sample, thus indicating the presence of organic acids before applying energy and thus indicating , also, the presence of oil-related substances in the sample (and material). Also or alternatively, simply measuring the pressure in the gas related to the sample can be indicative of a relevant change, so that a calibrator, meter or pressure device can be used in the method, either alone or in combination with mass spectrometry analysis (monitoring carbon monoxide can also be combined with mass spectrometry analysis or all three methods can be combined in the analytical method).
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65/164 [110] Such methods of the invention can also often be carried out desirably in the field, such as directly in a well or exploration site. Consequently, while many aspects of the invention comprise the use of small samples, in this and other methods, larger quantities of materials can be used, such as cup-sized containers, pint-sized containers, room-sized containers, storage containers, gallon size or containers that have volumes of about 5 liters or more, about 10 liters or more, about 20 liters or more or even about 30, 40 or 50 liters or more (for example, a large bucket of material sample). For example, a large cut container can be collected from where cuttings are deposited close to a well site (for example, in association with a well site stirring table) and then used directly for analysis with such methods.
[111] In addition or alternatively to light energy, other suitable types of energy can be applied to the sample in order to modify the gas content for direct evaluation or to check if the pressure increases, indicating a change in content that is indicative of the presence of target substance in the material. Examples of other types of suitable energy include methods of heating, vacuum, other forms of radiation (e.g., UV light) and the like. In another aspect, the method may also or alternatively comprise carrying out a chemical reaction to form such compounds which are indicative of the presence of the target substance in the material. The amount of energy applied in the practice of the method can be any amount adequate to achieve the desired change. In an exemplary aspect, the sample is heated to about 400 degrees C or more for a period sufficient to generate indicative target compounds (for example, carbon monoxide) from organic acids present in the samples.
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66/164 [112] The methods of the invention can and often include the step of subjecting a sample of the material, such as one or more cuts associated with one or more geological formations, to one or more forces to cause the release of a first gas containing an analyzable amount of one or more volatile substances. The force that can be applied to the sample can include a pressure force, such as a high pressure (positive pressure) or a vacuum; temperature; chemical reaction; application of radiation (such as microwaves, which can be used to remove water from the material); and / or physical forces, such as crushing or vibration (for example, ultrasonic vibration). Other forces that can be applied include dehydrating the sample by heat or chemical means, applying temperature to the sample, applying mechanical pressure to the sample, mechanically breaking part or all of the sample, subjecting the sample to a chemical reaction or a combination of any or all of them, optionally, in addition to applying one or more levels of vacuum and / or pressure to the sample.
[113] In one aspect, the force is a vacuum pressure, just like the vacuum pressures described above. For example, a low pressure can be applied to a sample of the material as a means to cause one or more volatile substances to be detectably released from the material (or a vacuum can be applied that could increase the release of one or more substances volatile substances or gas (or gases) in the sample if such a volatile substance is present). The exact amount of vacuum will vary depending on the material and other method conditions. Commonly, the pressure will be below atmospheric pressure, but greater than about 3x10 ^-4 millibar. In another aspect, practicing a method of the invention comprises applying a vacuum to the sample at a pressure that is between atmospheric pressure and about 1x10-3 millibar. In yet another aspect, the method comprises applying a vacuum to the sample at a pressure that is between the pressure
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67/164 atmospheric and about 25 x 10-3 millibar. In yet another facet, practicing a method of the invention comprises applying a vacuum to the sample at a pressure that is between atmospheric pressure and about 1 x 10-3 millibar. In yet another aspect, the method comprises applying a vacuum to the sample at a pressure that is between atmospheric pressure and about 1 x 10-2 millibar. In yet another sense, the methods of the invention may comprise a step of applying a vacuum to the sample which is defined by a pressure between about 1 to about 100 millibar.
[114] In other particular aspects, the method involves applying positive pressure to the sample. A positive pressure can be any pressure that is in excess of ambient atmospheric pressure and that results in a measurable release of the desired gas (or gases) (at least under conditions where the volatile substances that form such a gas (or gases) are present in the sample). Positive pressure can be applied by any suitable means, such as, for example, using a piston. The method may include one or more applications of positive pressure, or the combination of applying positive pressure with any of the other methods described in this document to assist in breaking the sample and / or extracting fluids from the sample. The specific pressure applied will depend on the other conditions of the method, such as the nature of the material and whether other forces are applied to the sample. In one example, a pressure of about 400 pounds (181.44 kg) to about 1814.37 kg (4000 pounds) is exerted on the sample (for example, about 453.59 kg (1000 pounds) at about 1587.57 kg (3500 pounds), although higher pressures can also be exerted using certain methods available in the art, such as hydraulic pistons.
[115] In another aspect, the method also or alternatively includes the application of a physical force, such as crushing, abrasion, thermal decrepitation, crushing and / or drilling. For example,
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68/164 materials can be carried in a sample container comprising a crushable portion, such as a crushable side wall, and the sample container can be subjected to crushing in order to promote the release of volatile materials. For example, as discussed elsewhere in this document, samples that are or that comprise cuts may include hydrocarbon materials contained in small cracks, pores and other structures, which are distinguishable from fluid inclusions, due to their exposure to the environment and / or the fact that they are characterized by not being hermetically sealed in an inclusion. These formations in geological material, which are also represented in sections taken from such material, may contain hydrocarbons, such as oil-related hydrocarbons, which are maintained in the geological material. The application of physical force, such as crushing, can assist in releasing such materials from such formations. The selection of parameters for these methods will vary with the nature of the material, other parts of the analytical method, etc. A typical exemplary method of the invention will comprise crushing samples, such as cuts, by about 400 pounds (181.44 kg) to about 1814.37 kg (4000 pounds), which can be achieved using some of the exemplary devices described in this document. .
[116] It should be noted that, in certain aspects of the invention, no force is applied to the sample. In other words, only exposure of the material to a release channel, such as a needle that penetrates a container in which a sample of the material is contained, can allow the gas to be exposed for performance of the next step in the method or flow to another container, portion of a device of the invention, or the like, in which such other steps can be performed. For example, in one aspect, the gas that is released from the sample will flow to a gas trap device, such as
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69/164 a trap of liquid nitrogen gas, so that a portion of the gas becomes trapped in the trap and subsequently can be released in a predictable manner.
[117] In one embodiment, the methods of the invention are characterized by collecting the sample in a sealed container and submitting the sample for an initial period at approximately the same pressure (for example, within 90%, 95%, 99% or more of the same condition) or exactly the same pressure (at least within the limits of detection and / or condition, such as atmospheric pressure without respecting the natural fluctuations in such pressure) in which the sample was sealed in the sample container, so that a majority of volatile materials are not lost when released from the container. This often means that the sample will initially be subjected to atmospheric pressure.
[118] In another aspect, in addition to or alternatively to sample crushing, by the methods described elsewhere in this document, the methods may comprise mechanically breaking some or all of the sample, subjecting the sample to a chemical reaction or performing a combination of any of them, alone or in combination with the application of crushing, compression or the like. In another facet of the invention, it is characterized by the lack of any step that includes application of heat (for example, an increase in temperature of about 25% or more, about 35% or more, about 50% or more, about 75% or more, about 100% or more, etc.) for a period of more than about 12 hours, such as more than about 6 hours, more than about 4 hours or more than about 2 hours.
[119] In one aspect of the invention, the method comprises isolating or “trapping a portion of the gas released from the sample by placing the released gas in contact with a“ trapping gas (which can
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70/164 is also simply to be called “an imprisonment).
[120] “Imprisonment means that the trapped gas is collected and maintained or retained in a device, medium and / or location. Trapping in the context of these aspects of the invention typically occurs in a releasable manner, and gas is commonly trapped so that parts of the trapped gas can be released from trapping in a predictable manner, such as when some kind of change is made to the condition of imprisonment. For example, in one aspect, entrapment is a material that binds to some portion of the gas and the gas is released by changing the conditions of the connection, for example, by increasing the temperature.
[121] In a preferred aspect, entrapment is a cryogenic trap, such as a trap of liquid nitrogen, that traps gases by freezing volatile compounds on a surface that has been cooled by liquid nitrogen or other cryogenic methods, thereby freezing the volatile compound to the trapping device or trapping medium. In such embodiments, the method may include the step of releasing volatile compounds from entrapment due to heating of entrapment, thereby releasing volatile compounds from entrapment in a predictable sequence for further analysis and / or treatment. Freeze-trapping can be operated under any suitable conditions. Typically, conditions will be selected based on the properties of the material to be trapped by the means or device used in the inventive method. In one aspect, entrapment is a material or device that is cooled to about minus 50 degrees C or less in carrying out the method (for example, about minus 100 degrees C or less, such as about minus 150 degrees C or less , such as about 190 to 200 degrees C, although, in some cases, colder temperatures can be obtained
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71/164 and employees). Commonly, cryogenic entrapment will be cooled to such a temperature before exposure of the gas released from the sample to entrapment. In this regard, as with some of the preferred devices described below for practicing the inventive methods, there may be one or more controllable valves that are used to expose the sample release fans to trapping in a controlled manner, and the method will correspondingly include the step of exposing the trapping to the sample release gas in a controllable manner, after such cryogenic cooling.
[122] Other types of imprisonment may also be suitable for carrying out the steps of the inventive methods. In one case, entrapment can be selective, in which it has the ability (or greater capacity) to selectively bind to certain materials and / or not to selectively bind to certain materials. In one case, for example, entrapment is selected so that it is selective so as not to trap water, carbon dioxide (or other compounds that can interfere with parts of the analysis, make the analysis more difficult and / or less accurate) and / or make the analysis take longer or cost more) and / or one or more organic acids, particularly if the analysis of organic acids is also a part of the method.
[123] Typically, however, the trap used in the inventive method is a non-selective trap, at least in relation to the target substances of interest. The term "non-selective entrapment in the context of this invention typically means that entrapment binds to all or substantially all volatile compounds present in the sample or all relevant volatile compounds that are present in the sample. The operation of such non-selective trapping can be contrasted with selective trapping, as can be found in gas chromatography (“GC), which binds
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72/164 to a particular compound or a class of compounds, but does not bind to other compounds. This does not exclude the application of GC technology in carrying out certain aspects of the invention, since aspects of the invention in which GC technology is used are described elsewhere in this document and, as indicated above, in certain cases, entrapments selective, such as using a GC material (or set of such materials), could be part of a trapping component of the invention, or could constitute trapping.
[124] In aspects where the gas is subjected to entrapment, material contained in or that is otherwise linked to entrapment can be considered to form an “aliquot that is used for further analysis according to various aspects of the invention.
[125] As noted above, gas trapping devices, means or systems, which can be used in various contexts of the invention, can be selective or non-selective. In one aspect, the gas trap is a non-selective trap, capable of capturing gas containing several different types of volatile compounds, such as a cryogenic trap that freezes volatile compounds to fix them in a medium. A trap of liquid nitrogen is an example of such a cryogenic trap.
[126] The gas released from the sample (or “first gas) will be allowed to contact the trap for any suitable period of time. The ideal contact time will vary with trapping, the gases that are present or expected to be present and other factors. For cryogenic trapping, such as the trapping of liquid nitrogen described above, the contact time between trapping and volatile substances can be relatively
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73/164 short, such as less than about a minute and commonly less than about 45 seconds, usually less than about 30 seconds and often as little as about 15 seconds, about 10 seconds or less than about 10 seconds (such as 7, 6 or even 5 seconds) will be adequate. In certain cases, entrapment will comprise a pumping function, as in the case where entrapment is a trap / cryogenic pump, which can occur by the action of freezing substances upon entrapment. In this respect, having conditions that cause rapid freezing can be important, since such rapid freezing removes volatile compounds from the atmosphere surrounding the sample, which will in turn cause more volatile compounds to be released from the sample (since the system works towards balance).
[127] However, the entire period in which the gases released from the sample are exposed to trapping will be significantly longer than these short periods, such as a period of about 10 minutes or more, for example about 15 minutes or more, about 20 minutes or more, about 30 minutes or more, about 40 minutes or more or about 60 minutes or more. The amount of exposure time depends on the pressure applied, the nature of the sample and other factors. When, for example, an attempt is made to release and analyze a more refractory substance in the sample and / or when bonding with a particularly difficult sample material, longer application times may be necessary, such as about 15 to about 30 minutes. However, in other respects, the amount of time that is applied is about 10 minutes or less, such as about 8 minutes or less, about 6 minutes or less, or about 5 minutes or less.
[128] In some cases, where the method is performed with cycles
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74/164 cycles can vary in terms of the amount of time the gas is exposed to entrapment. For example, in the first cycle of a method, the time may be relatively shorter, such as less than about 10 minutes, in which there may be more gas readily available in association with the cycle, while in subsequent cycles, in which it is more difficult to extract gas from the sample, a longer period of time can be employed, such as about 10 minutes or more, to allow the gases of the second cycle to bind sufficiently to the trap.
[129] In aspects where an extended time before heating the liquid nitrogen trap is provided, the extended time is not just to provide more time for the gases to attach to the liquid nitrogen trap, but instead, such time extended sample can provide improved extraction or release of volatile species from the sample. Thus, the release of volatile gases from a sample can be, at least in some respects, considered dependent on the variables of the nature of the sample, the nature of the volatile products, the forces applied on the sample to promote the release of such volatile products and the time given to allow such release and / or gas collection. It is often preferred that all volatile fluids that are gaseous in the sample are collected before exposure to any vacuum. When the sample contains volatile liquids, applying a vacuum to the sample, such as after “passive (no vacuum) collection of gaseous volatile substances from the sample, may be desired, as such a vacuum application can lead to the boiling of substantially all or all such liquids or at least result in the boiling of a substantial proportion of such volatile substances (at least 20%, at least 30% or at least 33% of the quantity); a majority of substances; a substantial majority of substances (at least 66.66%, at least 75%,
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75/164 at least 90%, at least 95%, at least 99%); or at least a detectable amount of such substances. In any case, the boiling of such volatile products that are normally liquid (at atmospheric pressure and typical ambient temperature) will make such substances boiled or the boiled fraction of such substances gaseous. The length of time required to reach a desired boiling level of liquid substances in the sample depends on factors similar to those described above in relation to the release of gaseous volatile compounds, but will mainly depend on the weight of the substance (heavier materials typically exhibit more time to enter boiling). The application of longer periods of vacuum, and resulting boiling, can thus result in the conversion of a significant amount of liquid volatile products into gaseous species for analysis in accordance with the methods of the invention described herein. Thus, certain aspects of the invention comprising the application of extended periods of time to release gaseous volatile substances from a sample and / or the application of vacuum to bring liquid volatile compounds to a boil in a sample provide the methods of the invention with a unique advantage in relation to the prior art due to the fact that more of the volatile substances in a sample can be completely analyzed allowing the time necessary for more of the volatile liquids to be released and / or captured.
[130] In one aspect of the method, the change in temperature used to release gaseous species from liquid nitrogen trapping is accomplished in less time than rapid heating methods used in gas chromatography (GC) methods that also use liquid nitrogen trapping. Such GC methods use “instant or rapid heating applied to a trap of liquid nitrogen used in the GC method, which releases many, most
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76/164 partly or substantially all gases trapped in the trapping of liquid nitrogen at once. GC methods also require that all gases to be analyzed enter the GC medium simultaneously, just like a trap if used in the method, almost simultaneously, since the presence of all gases to be analyzed at the same time is necessary for the effective performance of such analytical methods. These limitations are not typically necessary (or desired) for the methods of the invention described in this document and, as described elsewhere, a gradual heating of the trapping of liquid nitrogen over a longer period of time to allow for the predictable release of trapped gases it is a common aspect of the methods of the invention that comprise a trap, such as a trap of liquid nitrogen. In addition, it denies the need for any type of gas separation other than heating the liquid nitrogen trap in these aspects of the invention. Thus, in another facet of the invention, the invention lacks any molecular selection step, such as molecular distillation or similar method, which is carried out on the substances to be analyzed in the method.
[131] In some respects, a relatively high vacuum can be applied to a trap or applied to the device or system used to perform the method of the invention so that the trap is under vacuum conditions for a period of time. For example, in some cases, where a relatively high vacuum is applied to a sample, this vacuum can also be applied through other parts of the system, including trapping. In other respects, the method also or alternatively comprises a method in which a vacuum is applied to capture non-condensable gases and remove such material from contact with entrapment
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77/164 (or to achieve at least substantially such a state).
[132] In certain respects, such as where relatively high vacuum is applied to entrapment or the system so that a vacuum condition is present in the entrapment for a period, it may be advantageous to continue to reinforce the entrapment medium or device with any that is the substance used to trap the target gases, so that gases that can be easily / readily released from the trap are kept in contact with the trap. For example, in the case of a liquid nitrogen trap, the method may comprise continuously applying liquid nitrogen to the trap while the vacuum condition is present in order to keep the substance of interest (eg, ethane, ethylene, etc.) trapped in the imprisonment until they are ready for release in a predictable manner.
[133] Another action that can form part of the methods of the invention is the step of isolating the sample aliquot. Commonly, once the gases are collected from the sample to form an aliquot, this aliquot can then be isolated from the sample, so that the rest of the method analysis or at least this step or part of the method is conducted on the aliquot without additional collection of sample gas for the collection of this rate (or if this is the final rate or only a single rate is being collected for the particular application of the method). This isolation method can be performed for many reasons and using any suitable technique. When devices of the invention described elsewhere in this document are used in the practice of the method, for example, one or more valves can be engaged, which results in isolation of the gas from the sample aliquot. The method may also or alternatively include the step of isolating the trapped gases from access to other
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78/164 components of the device or system where the trap is located. For example, when the method is performed with a device of the invention comprising (a) a sample holding unit, (b) a gas trap and (c) a mass spectrometer, the method will typically comprise the step of isolating the gas trapping of both the sample holding unit and the mass spectrometer for one or more periods of time (for example, isolating the trapping of the samples after sufficient time has passed and / or applying conditions necessary to collect sample gases and isolate the mass spectrometer until it is time to release the trapped gases for analysis).
[134] In aspects of the invention where one or more gases released from the sample are trapped to form an aliquot, the method typically includes the step of releasing volatile substances from the aliquot as gases released from trapping in a predictable sequence. For example, when the sample is comprised of one or more drilling cuts obtained from an oil well site, gas is obtained from the cuts, passively or by applying one or more forces, such as mechanical crushing and / or applying a or more vacuum pressures on the sample and then subjected to a trap, such as a trap of liquid nitrogen. Much of the gas in the cutting samples will be captured by trapping. Allowing the trap to heat, passively or, more typically, by applying heat, directly or indirectly, to the trap will allow the volatile substances in the gas that are frozen to trap to be released in a predictable manner.
[135] A “predictable way means that substances, such as individual volatile gases or mixtures or other types of species
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79/164 volatile gases are released from entrapment in such a way that, if gases are present, their release can be predicted from the timing and / or condition of their release. For example, in one aspect, a predictable way means that different species are released as a function of time. In many respects, the release of species can overlap the release of other species, so that, for example, there may be a first release period for one or more first species (for example, lighter or more volatile compounds), a second period in which there is a release of one or more second species (for example, heavier and less volatile compounds) and an intermediate period in which both one or more first species and one or more second species are being released. In many respects, there will be several such periods and interim periods. Intermediate periods and periods can, however, form a predictable release pattern so that, if expected compounds are present in the sample, the expectation that they will be released at a certain time and / or under the application of a certain condition.
[136] Another stage of the methods of the invention also or alternatively that analyzes gases that are directly released from the samples, typically, after applying an energy to the gas, to break down (decompose) the substances in the gas, thus making the species volatile in the gas to target analytical substances. For example, such a method of the invention may comprise taking a volume from a sample, such as cuts, optionally applying one or more forces to the sample in order to release one or more endogenous volatile gases (such as formic acid, acetic acid, carbonic acid; or other organic acid), apply a source of energy to volatile gases in order to break down volatile species into one or more target compounds
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80/164 (such as carbon monoxide) and analyzing the target compounds to determine whether endogenous volatile substances were present, particularly if the presence of such endogenous substances is indicative of the presence of petroleum or other material that is desired. In such methods, optionally no trapping of a gas is performed and / or no mass spectrometry or similar method is applied. This aspect of the invention provides simple methods that can be readily performed with limited amounts of equipment, while still providing a sufficient indicator that oil or another target substance is in the relevant formation associated with the sample.
[137] The amount of energy to be applied can be any adequate amount of energy and / or strength to break down the volatile substances in the target substances. In one aspect, the invention comprises applying heat of about 400 degrees C or more or another temperature or condition in order to disassociate formic acid, carbonic acid or both (in one aspect, carbonic acid only) and one or more components thereof, such as carbon monoxide and / or carbon dioxide. In another aspect, the method comprises applying a vacuum to the sample to assist or deal with the breakdown of endogenous volatile substances in the target gas (or gases). The vacuum conditions described elsewhere in this document have been associated with such a breakdown of endogenous gases and can be applied in this regard as well. In yet another aspect, the invention also or alternatively comprises placing the sample in contact with one or more chemicals that assist in the release of target gases from endogenous gases, such as application of a desiccant. Another aspect includes the application of radiation, such as microwaves, to the sample, to assist the breakdown of endogenous gases.
[138] The methods of the invention also include the step of
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81/164 analyze gases generated or released in the various methods (for example, gases released from entrapment or decomposed gases generated in which no entrapment is carried out), in order to determine whether the substances of interest are present in the formation or material of which the sample was taken or with which the sample was associated. Any suitable type of analysis can be applied to such gases and any suitable combination of methods can be applied as well, if desired and possible.
[139] A preferred aspect of the methods of the invention described in this document comprises the application of mass spectrometry analysis for gases released from entrapment. Any suitable type of mass spectrometry method can be used in this regard.
[140] When performed in the practice of the invention, a mass spectrometry method will typically be selected to be suitable for the identification of expected or desired target substances. For example, if the desired task is to identify the presence of hydrocarbons relevant to petroleum and / or organic acids and / or inorganic gases (for example, H ₂ S, helium and CO ₂ ) in cut obtained from an oil well, 0 spectrometer of mass will be selected and operated so that it can identify, among other things, volatile gases, such as octanes, nonanes and larger hydrocarbons, which are indicative of the presence of oil in the geological formation from which the cuts originated. Mass spectrometry is typically a preferred method as it works quickly and provides a useful and detailed level of analysis. There are a variety of mass spectrometry devices that can be used to perform methods that involve mass spectrometry. A quadrupole mass spectrometer (residual gas analyzers (RGAs)), for example, are readily available devices, which may be suitable for
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82/164 many of the methods described in this document. Flight time mass spectrometers, which provide rapid analysis, can also be suitable in many cases. More complex systems, such as mass spectrometer / mass spectrometer (dual dual mass spectrometer / triple quads) could also be used in some cases and can be advantageous to better separate substances with masses that are similar to other substances that may be present .
[141] Mass spectrometry is not a required component of the invention, however, like other analytical methods, it can be used to analyze samples in accordance with the invention. Flame lonization detection could be used for analysis of several hydrocarbon species. Gas chromatography can also or alternatively be used to analyze gases in certain aspects of the invention. It may also be or alternatively possible to analyze hydrocarbons via infrared spectroscopy or Raman spectroscopy.
[142] Other times, simpler methods may be used in place of mass spectrometry or such sophisticated methods, such as gas chromatography. In important aspects of the invention, the invention comprises detecting the formation of target substances that are released from organic acids, such as carbon dioxide or carbon monoxide, which can be detected using conventional commercially available detection devices or the technology in such devices. Pressure release, for example, can also or alternatively be used as an indicator in some methods. The release of water could simply be measured using a moisture meter and, also or alternatively, provide relevant information on certain aspects of the invention.
[143] Although the methods of the invention can be carried out with
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83/164 various approaches, in some aspects, the methods can be characterized by steps that are not carried out and / or the components that are absent from a device or system of the invention. For example, one aspect of the invention is characterized by the lack of any gas chromatography step in the method (or, correspondingly, by the lack of such a device / component in the system / device of the invention). Other steps that can be excluded from the methods of the invention include infrared analysis. It will be understood that, in general, the principles described in this document in relation to the methods of the invention will be implicitly transferred to the devices and systems of the invention, so that this description could also be interpreted as devices and systems of the disclosure that lack capacities of infra-red.
[144] In aspects of the invention where a trap is used, another optional step of the method of the invention is collection and analysis of non-condensable gases (ie, gases that will not condense and safely bond to the trap and / or other sample materials ) (“NCGs). In some aspects, the application of one or more other steps of the method can generate materials that will not bind to the gas trap. For example, when a liquid nitrogen gas trap is used, some materials may not be very volatile and / or some gases may not bond to the trap or at least not bond to the trap completely or bond to the trap in sufficient quantities to indicate an accurate amount of the material or even indicate the presence of the material in the sample. In such cases, the method may include collecting non-condensable materials and / or unbound gases. These materials can be collected, such as by applying a collection method to isolate such material for further analysis. In the use of devices of the invention, the device may include a mechanism for collecting such materials from
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84/164 a way that isolates them from the rest of the material to be analyzed. A vacuum can be applied to gases that are not connected by trapping, for example, to collect such gases. Ideally, such gases are isolated and captured in a container or structure that functions as a container in a device and then selectively subjected to analysis before or after analysis of the trapped gases. In some respects, the NCG material may be too large for analysis, and the method will comprise a step of limiting the amount of NCG material that is analyzed and / or controlling the rate of analysis of the NCG material.
[145] In some respects, the methods of the invention may include the step of repeating several steps of the method. For example, in one aspect, the invention provides methods that comprise a cycle of repeatedly applying one or more forces to the sample to cause or assist in the release of volatile compounds from the sample. Such methods may include repeated application of the same type of force or application of two or more different forces or application of the same type of force, but in a different amount, duration, etc. For example, in one aspect, the invention provides methods in which vacuum is applied to the sample several times, at different pressures, for different periods, or both. In some respects, gases that are expected to contain volatile products under this condition are the target of one or more analytical methods practiced on gases or trapped gases generated from the gases released from the sample. Such methods will typically also include multiple steps to capture multiple aliquots of gas generated by applying the multiple forces, releasing the respective gases and analyzing such released gases, which can then be examined in combination to obtain a sample profile.
[146] The analysis of substances by the methods of the invention can
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85/164 be qualitative (determining the presence, but not the quantity), quantitative or both. The methods of the invention in which trapping and predictable release of trapped gases occur are particularly receptive to quantification. In one aspect, the invention provides a method that is capable of quantifying the amount of one or more volatile compounds contained in the sample. Quantification can be performed through analysis against a standard. For example, a pattern of a gas in a known volume and known pressure can be generated, and a sample can be compared to this pattern. Similarly, a drop of a liquid of known volume and composition can be analyzed by the method employed and then the result (or results) of the sample (the samples) in comparison to such a standard. Standard compositions are typically comprised of an NCG, such as nitrogen (for example, at least about 80% is nitrogen or at least about 85%, at least about 90% or more of the standard is nitrogen and / or methane) , with the small remaining amount comprising a known quantity of one or more hydrocarbons, which will be released from trapping at different temperatures and allowing for rapid analysis of the standard material. Due to the fact that patterns may not be contained in a material, such as cutting, the method may comprise controlling the volume and / or release rate of analyzed material (for example, using a needle or restricting the passage to control the flow sample material to the analytical components of the system).
[147] The methods of the invention may comprise analyzing the sample for the presence of organic acids and / or hydrocarbons, with the analysis of the presence of organic acids (which is typically done by analyzing the presence of other target substances, such as carbon, which indicate that such organic acids are present) typically are preferred or selected if
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86/164 only one of the two is analyzed. However, hydrocarbon analysis can also be important. For example, the analysis of C5-C10 hydrocarbons in the sample can provide information on the entire volume of oil in a formation, since the presence of oil is established by identifying target substances that indicate the presence of organic acids associated with oil ( for example, formic acid and / or carbonic acid or just carbonic acid). When samples sealed in the well or other collection site are analyzed in the method of the invention, the hydrocarbon data can directly correspond to the presence of oil in the associated formation. In the case of old unsealed samples, hydrocarbons are likely to be associated with fluid inclusions only, and the presence of hydrocarbons in just such materials may not be sufficient to precisely identify the presence of oil in the formation in question.
[148] In one aspect, the analytical method comprises analyzing the amount of water in the analyzed gases (for example, the gas released from entrapment in a method in which gases are trapped and released). It was surprisingly found that a high concentration of water (in geological material and / or in a sample of such material) can be an indicator of oil saturation. Although without sticking to any particular theory, it is believed that one or more organic acids, such as carbonic acid, formic acid and / or acetic acid, which are present in cuts or samples will break in the performance of certain aspects of the method of the invention, thus generating more water that would normally be present in the sample (for example, from analysis of such cuts by extracting gas from them containing volatile compounds, capturing such gases in a liquid nitrogen trap, releasing such gases from nitrogen trapping in a predictable manner, such as through accelerated heating of the
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87/164 trapping liquid nitrogen and subjecting the released gases to mass spectrometry analysis). However, in other aspects of the invention, compounds other than water are also or alternatively analyzed to evaluate the sample. This is particularly true since other organic acids associated with the samples may not release water.
[149] In one aspect of the invention, the detection of excess water associated with a sample as an indication of oil-associated hydrocarbons is performed under conditions where excess water associated with petroleum compound in the sample can be detected and distinguished from another water in the environment. For example, in aspects of the invention where a trap of liquid nitrogen is used in the method and / or incorporated into the device / system of the invention, the observation of water at temperatures below which the release of normal water is expected. So, for example, in one aspect the method comprises detecting water at a temperature that is significantly colder than -55 degrees C (a temperature that represents about the lowest temperature at which water would typically be expected to be released and detected ), such as a temperature of about -70 degrees C or less (cooler), about -80 degrees C or less, about -100 degrees C or less, about -110 degrees C or less, about - 120 degrees C or less or even colder temperatures, such as about -130 degrees C or even about -140 degrees C (for example, about -100 degrees C to about -200 degrees C, such as about - 120 degrees C to about -180 degrees C). In experiments conducted with systems of the invention, such as the system exemplified in Figure 1, water can be detected when released at temperatures of around -140 degrees C (a temperature normally associated with a peak / release of carbon dioxide) and at higher temperatures (present in the
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88/164 system when the system is allowed to warm or is heated by the application of heat from heaters on or over the system), but above -55 degrees C. Typically, the detection of water by a mass spectrometry system will occur at a plurality of distinct peaks associated with such temperature increases, in the range of about -140 degrees C to about -55 degrees C in such a system / device. Without sticking to the theory, it is believed that the detection of water under such abnormally cold conditions reflects the breakdown of organic acid compounds during or after release from entrapment and / or water generated by acid decomposition by ion fragmentation resulting from electron bombardment under high vacuum in the mass spectrometer. In any event, the detection of water under such cold conditions, especially when combined with conditions that could lead to and / or allow the decomposition of organic acids associated with the samples, such as cuts associated with an oil well, is another important aspect of the invention.
[150] In particular aspects, if the evolution of water (generation) caused by acid decomposition occurs during, or after, acid release from liquid nitrogen trapping, then part of the water, but typically less than all the water, created by acid decomposition it can be trapped again in the trapping of LN2, but the rest of this newly formed water escapes from trapping and is analyzed. Other non-condensable gases that form acid decompositions, for example, acetic acid methane and formic acid carbon monoxide, are typically not trapped back in the trap, but are usually transported and analyzed on the mass spectrometer by evolution of the acid of imprisonment.
[151] The separation of water developed from the breakdown of normal water acid via evolution of a trap, for example,
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89/164 a cryogenic trap, such as a trap of liquid nitrogen, has not been previously described by others, and this phenomenon is an exclusive advantage of this invention. As discussed in this document, the mapping of acids associated with oil and gas using water and other indicator compounds is a unique feature of this invention and has many applications for oil and gas exploration and production.
[152] In yet another aspect, the method comprises a P2O5-based analysis of the water content of one or more samples analyzed in the method. The gas in a sample (typically after heating to extract water from the rock before the gas is released) can be transferred around / over an apparatus or container containing P2O5 (with a known weight) and the weight, therefore, measured to determine the quantity of water present in the sample. Such methods can advantageously be performed on water in fluid inclusions as part of the method of the invention, since water can be difficult to analyze in the context of analyzing fluid inclusions.
[153] In one aspect, the method includes using hydrocarbon-containing fluid inclusions as a negative indicator of the presence of oil. In certain aspects, the presence of hydrocarbon-containing fluid inclusions is a negative indicator of the presence of oil in a material and the presence of a low number of hydrocarbon-containing fluid inclusions, in particular, immediately adjacent, usually overlying, an inclusion zone abundant oil and gas fluid is typically indicative of a high chance of oil in the material. Such an analysis can be included as part of the methods of the invention described herein and, in and of itself, represents an aspect of the invention. Thus, for example, the invention provides an oil production zone mapping method alone or in combination with other methods that examine 0
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90/164 number of hydrocarbon-containing fluid inclusions in a material and identify areas where the number of oil-relevant hydrocarbon fluid inclusions is relatively low (less than about 10% of the number, for example, less than about 5 % of the number, of fluid inclusions in areas associated with water, such as a water segment) or undetectable as areas that have a high probability of representing oil production zones. This is obviously not true for pore fluids (fluids currently present at the site), which can be analyzed by other aspects of the invention.
[154] In another aspect of the invention, the method comprises the step of analyzing gases released for carbon dioxide. Carbon dioxide, like water, can be produced from the breakdown of organic acids contained in the sample. In other respects, this step is avoided, as it may also be or alternatively be the case in relation to analyzing water generation. This is due to the fact that any substance, and particularly carbon dioxide, can be confused with other sources of the substance, which can make the analysis more difficult. However, in certain cases, the analysis of carbon dioxide in the gases analyzed is an aspect of the invention.
[155] In another aspect, the methods of the invention may comprise analyzing the analyzed gases for the presence of carbon monoxide, which may be an indication that formic acid is present in the sample (and thus useful in mapping production zones of oil). Carbon monoxide can be detected using conventional carbon monoxide detection devices, which are commercially available or using technology similar to that used in such devices. Carbon monoxide detection can be used to identify production zones within a well, where areas of a well associated with a quantity
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91/164 relatively high carbon monoxide indicates the presence of oil in such an area (for example, at a certain depth in a well). Within a well, the presence of about 35% or more, such as about 50% or more of the maximum detected amount of carbon monoxide (which can be defined as 100%) is typically indicative of an amount relevant to petroleum from carbonic acid and / or formic acid, typically formic acid, in such a site (in some cases, the method is focused on identifying the presence of carbonic and / or formic acid, typically formic acid, which will be indicative of the presence of oil in the sample and related material).
[156] In another facet, the invention provides methods for determining the permeability of a formation or composition. Such methods typically require a multi-sample method applied to samples under different conditions, such as different pressures, in order to assess the permeability of the sample (and, correspondingly, the formation).
[157] Such methods are typically performed with main samples and entirely containing volatile non-fluid inclusion substances. In other respects, the methods are performed on materials that comprise fluid inclusions.
[158] A sample can, for example, be subjected to different pressures to release different aliquots, and each respective aliquot analyzed for one or more substances, such as hexane (or methane, propane, pentane, etc.). The relative quantities of the target material released under both conditions are analyzed with the output of the analysis which is indicative of the permeability of the sample (and thus the formation). The analysis of such methods may at first seem counterintuitive, due to the fact that many samples, such as cuts, can be highly permeable, relatively impermeable or contain zones of both high and low permeability. For example,
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92/164 in relation to hexane, if the application of a first and relatively weaker vacuum results in a relatively large amount of hexane being released from the sample and analyzed (in comparison with the second aliquot performed under a stronger vacuum), this result will typically be indicative of low sample permeability. This surprising result is due to the fact that most of the petroleum-related hydrocarbons that could be lost at the first rate in such material will be lost between the generation of the sample (for example, the drilling that produced the cut) and the analysis of the sample for high permeability samples. Therefore, if a larger amount of hexane or other relevant target substance is released and analyzed when the first vacuum condition is applied, such a result indicates that the sample permeability is relatively low, due to the fact that hexane was not lost between the sample generation and analysis. If the sample has relatively higher permeability, it will typically release more hexane when applying a strong vacuum, due to the fact that only the material in the sample with low permeability will release hexane at such a time. Thus, the proportion of hexane or other target substance released from a first aliquot and a second aliquot by methods of the invention can be compared to provide an indication of sample permeability is another aspect of the invention. The other gases analyzed in addition to hexanes can also be used to assess permeability. In fact, it may be useful to study the relative permeabilities of the various volatile constituents in the sample.
[159] In other respects, permeability can be assessed by infusing the sample with a substance, such as noble gas, and then measuring the release of this infused substance, alone or in combination with the release of endogenous volatile substances , such as hexane.
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93/164 [160] In one aspect, the invention provides a method for determining the permeability of a material by comparing the release of one or more volatile substances and / or classes of volatile substances from the same sample of the material under two or more conditions different conditions that promote the release of volatile substances from the sample, such as applying two different pressures to a single sample. In some respects, this process is applied to a plurality of samples, such as at least 10, at least 20, at least 50, at least 100, at least 250, at least 500 or even at least 1000 samples. In some facets, at least three conditions, at least four conditions, at least five conditions or more are applied to a single sample to assist in the assessment of permeability.
[161] In an example of the permeability assessment method described above, a first aliquot is extracted from a sample, such as a cut from an oil well, at a pressure of about 50 millibar. A second aliquot can then be extracted from the same sample at a pressure of about 5 millibar. The permeability can then be estimated by comparing the data obtained from these two analyzes. In other words, the force required to extract volatile products from a sample can assist in determining permeability. This is of additional significance due to the fact that conventional permeability measurements can be performed on cut samples, but instead are typically applied to conventional core or rotating sidewall core samples and are based on the pressure required to push a fluid through a uniformly shaped piece of rock, usually a cylinder. Typical fluids used in conventional permeability measurements include helium and mercury. Such permeability measurements cannot be applied to well cuts as they require a consistent volume of intact rock.
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94/164 [162] A formula that can be useful for estimating permeability using hexanes in accordance with the aspects described above of the invention is: 100 * (hexanes ^{aliquot 2} -hexanes ^{aliquot 1} ) / (hexanes ^{aliquot 2} + hexanes ^aliquot1 . one aspect, this formula is used to determine permeability. Values obtained from this expression range of 100 to -100. A value of 100 indicates that hexanes were only obtained from aliquot 2 in an analysis of 2 aliquots without hexanes analyzed in aliquot 1, these are the most permeable samples.A value of -100 indicates that hexanes were only obtained from aliquot 1 without hexanes analyzed in aliquot 2, these are the least permeable or very little permeable samples.
[163] The nature of the calculation reflects an unexpected aspect of the invention. Normally, the most permeable samples could be expected to have high levels of hexanes in aliquot 1 and low levels of hexanes in aliquot 2. This, however, is not the case. It was surprisingly found that, in the most permeable samples, the most easily removed hexanes are lost between the moment the rock is broken by the drill bit and its elevation to the surface suspended in the drilling mud, until the sample is sealed in a brass tube at the well site or at some later time. However, the most permeable samples show the lowest amount of hexanes in aliquot 1 and the highest amount of hexanes in aliquot 2, in the type of method described here. Thus, a sample showing high levels of hexanes in aliquot 1 and low levels of hexanes in aliquot 2 is a sample with very low permeability so that hexanes are not predominantly lost from the sample by disaggregating the drill bit and transporting to the surface in drilling mud in standing time under atmospheric conditions before being sealed in a container, such as a brass sample tube, and analyzed.
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95/164 [164] The permeability in samples analyzed according to these aspects of the invention can vary as a function of the size, shape, mass and chemical affinities of the compound. It is therefore instructive to consider a permeability range using several of the compounds that are analyzed or all of the compounds that are analyzed. Hexanes can be a preferred measure of permeability for the method (or inclusion in the method) due to the fact that, under natural conditions before analysis, hexanes must be liquid. And, under all analytical conditions used in the present analysis, hexanes must be gaseous. This then removes any possibility of confusing boiling with permeability.
[165] As mentioned elsewhere in this document, in some respects, the method of the invention comprises analyzing the presence of hydrocarbons. In some cases, the method comprises the analysis of short-chain hydrocarbon molecules. In other respects, the method comprises analyzing long-chain or short-chain hydrocarbon molecules. For example, C2-C15 hydrocarbons, such as C2-C12 hydrocarbons, for example, C2C10 hydrocarbons, can be trapped and analyzed using a cryogenic trapping method, and methane can be collected and analyzed using NCG methods described elsewhere in the present document.
[166] The analysis of long-chain hydrocarbons is another facet of the invention that distinguishes it from prior art methods, which are typically performed very quickly and thus are unable to analyze such materials effectively, because such methods do not sufficiently cause longer-chain hydrocarbons to be released from the samples. When a longer period of time is used to trap materials, such as when a trap / cryogenic pump is used for about 10
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96/164 minutes or more, such as about 12 minutes or more or about 15 minutes or more, relatively long chain hydrocarbons can be captured and then analyzed by the method, which is another distinguishing feature of such techniques in the art previous. Relatively long chain hydrocarbons means hydrocarbons comprising a main chain of six or more carbon atoms, such as seven or more carbon atoms or eight or more carbon atoms.
[167] In another aspect, the invention comprises consideration of pressure changes in the performance of the method. The methods of the invention may comprise the breakdown of compounds, such as organic acids (for example, formic acid, carbonic acid or acetic acid) into other compounds (for example, carbon monoxide and water in the case of, for example, carbonic acid, or methane and carbon dioxide in the case of, for example, acetic acid), which can result in changes (typically increases) in pressure in the system due to the generation of such non-condensable gases (carbon monoxide and methane).
[168] In yet another facet of the invention, methods are provided in which changes in hydration are carried out on samples, particularly after such samples are subjected to conditions in which organic acids, such as formic acid or carbonic acid, can be formed, particularly at from materials present in the sample. For example, in one aspect the method comprises subjecting the samples to conditions that can form carbonic acid, which can be associated with and / or can also be broken under such conditions or other conditions achieved in the performance of the method to form water, in which the presence of such generated water is indicative of carbonic acid or formation of carbonic acid and thus indicative of the presence of oil-related hydrocarbons in the sample (and the
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97/164 material). For example, subjecting oil well cuts to methods described in this document in which gas is released from the cut, such as under varying degrees of vacuum pressure, trapped by a trap of liquid nitrogen or a similar device and released from such trap for mass spectrometry analysis, water can be formed, and such water can be detected by any type of conventional method, including moisture or hydration detection techniques that are known in the art. The detection of water can, in some contexts, provide an indication that oil-related hydrocarbons are present in the sample and material and thus the method may comprise performing an analysis for changes in hydration, moisture or otherwise detecting changes in content of water, after applying such methods or forces to the sample.
[169] In another aspect, the invention comprises analyzing the effects of pressure on formation by examining the sample for effects of formation pressures. In such aspects, typically, several samples of different areas or depths are obtained and examined for changes in fluid composition, which may be indicative of a distinct / large change in hydrostatic pressure between different formation areas (for example, a usually high pressure zone for normal pressure or from normal pressure zone to usually low pressure zone), which may be relevant to how the materials in the formation will behave under different conditions.
[170] Any of the analytical methods described in this document that can be applied to the gases analyzed in the methods of the invention can be, and often are, combined, to provide a more complete analysis. For example, in one aspect, the method includes the step of analyzing the analyzed gas for the presence of carbon monoxide, increased water content and / or the presence of C5
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C10 hydrocarbons. In another exemplary aspect, the method comprises analyzing the analyzed gas for the presence of carbon monoxide and carbon dioxide.
[171] The methods described above can be practiced with or without the application of other methods used for the identification, evaluation and / or characterization of formations and / or materials in them, such as the oil content of a formation. For example, in one facet of the invention, the methods of the invention described in this document are applied without carrying out conventional fluid inclusion analysis or gas chromatographic analysis of the material or sample. However, in another dimension, the methods of the invention can be performed in combination with such other conventional analytical methods, in order to potentially enrich the information gathered about the material. Another method that can be combined with these methods is to examine samples for fluorescence data that can provide evidence of sample oil staining.
[172] In an exemplary aspect, the invention comprises combining information gathered from the main methods described in this document with information gathered from fluid inclusion analysis. The methods for performing fluid inclusion analysis are described in earlier patents referred to and described elsewhere in this document. In an aspect that can be particularly advantageous in certain contexts, the method comprises performing a fluid inclusion analysis which comprises analyzing oxygen trapped in fluid inclusion, nitrogen or a combination of them, which are associated with the material. These non-condensable gases can provide information on the paleontological surface (paleoexposure) of the material, which can assist, for example, in oil exploration.
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99/164 [173] In yet another aspect, the methods are practiced in combination with gamma ray mapping, for example, identification of types of geological formation, for example, identification of areas vs. shales. It includes gamma ray mapping as a component of the analytical method can determine the nature of the formation material (sand vs. shale). The size of a formation may be relevant to assess whether the deposit of the material (for example, oil) is of sufficient quantity to be economically advantageous to produce the material (again, typically oil) of the formation.
[174] In another more general sense, the invention provides methods for analyzing the content, such as the organic acid content and / or the water content, of cuts that were closely associated with drilling muds, for example, to perform mapping oil production zone. In fact, the generation of oil production zone mapping is a preferred and particularly advantageous application of this and other methods of the invention. Most oil well site cuts will be closely associated with drilling muds (one exception is an air-drilled cut). It has been found that such cuts can provide an exclusive opportunity to analyze drilling areas. Although without adhering to any particular theory, it is believed that the interface between such cuts and drilling muds will form physiochemical structures that retain the levels of organic acid and possibly other levels, due to the normal differences in pH of the respective materials (mud and cuts ). Consequently, methods of oil analysis and production zone mapping which comprise preferably using such materials are an important aspect of the present invention. The methods that can be used to analyze the organic acid content of such cuts can be any of the methods that are described herein or are otherwise known in the art. What characterizes the methods
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100/164 of this particular aspect of the invention is that the method, at least in part, focuses on cuts that have had intimate interactions, thus probably forming such unique conditions to maintain their organic acid content. Again, the application of the methods of this invention to determine the organic acid from such cuts is particularly useful in production zone mapping. This is due to the fact that such organic acids are typically in cuts that are colocalized with oil in many geological formations.
[175] One of the advantageous aspects of the methods of the invention described in this document is the application of the invention (such as the analysis of organic acid content) using samples obtained from fresh water environments (environments in which the water associated with the majority, substantially all or all samples analyzed contain little or no salt). For example, in certain aspects, the method is carried out with water having a saline content less than about 10,000 ppm, such as less than about 5000 ppm, such as less than about 2500 ppm. In this sense, the organic acid content analysis methods of the invention can work under conditions where conventional well profiling methods fail, due to the nature of the fresh water (low saline content) present in such sites.
[176] In yet another aspect of the invention, mud-associated cuts have retained or captured water / brine from the site where the cuts are generated, and the method comprises analyzing the water / brine associated with such mud-associated cuts, for example, by analyzing conductivity of such water / brine is determined. Again, most of the cuts will be associated with mud when taken from oil drilling sites.
[177] These amounts of water / brine are typically small and the method may comprise freezing such
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101/164 microquantities of water and then subject them to a suitable method for analysis, such as scanning electron microscopy with energy dispersive X-ray fluorescence, electron microprobe and / or an ion probe, or other suitable method , to analyze the water / brine composition of the water in such cuts. Such data can be used by petrophysicists to assess oil and water saturation in a well as currently determined by conventional well profiling methods. This and other such information that is obtained from such mud-associated cuts can be used to map the presence of oil and other substances from such samples, and thus can be used as another method to perform “production zone mapping, in accordance with the invention. In one aspect, the method comprises only analyzing such a brine / water content. These methods can be particularly important in that resistivity (which is currently successfully based on the presence of brine in a material) is currently used commonly as a key quantifier of oil content in drilling sites and other geological formations.
[178] The methods of the invention that involve the analysis of volatile substances can be performed with any number of aliquots taken from any suitable number of samples. In some cases, it may be advantageous to take a single aliquot of each sample in a set of samples. Thus, the invention provides a method in which a suitable sample is provided, the sample is subjected to or exposed to forces that cause the release of a gas containing an analyzable amount of one or more volatile substances, and the method includes the capture step ( for example, trapping or concentrating) a first trapping gas (such as a condensable gas in a system based on gas condensation) in or with a medium or other means in an analyzable amount for
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102/164 generate an aliquot, optionally, but typically, isolate the sample from the aliquot and, optionally, but typically, release at least an analyzable amount of volatile substances from the trap or collection means and subsequently analyze at least one aspect of the chemistry one or more volatile substances released. Often, this will be the case where the “single rate will actually comprise a condensable gas component (sub-rate) that is trapped with a first trap and a non-condensable gas component (sub-rate) that is typically collected separately and / or analyzed separately from the condensable gas sub-rate.
[179] The forces applied or to which the sample is exposed can be any suitable forces, such as those described above. In a set of facets, the method comprises subjecting the sample to a pressure of at least 1 millibar and less than 1 atmosphere, such as between at least 1 millibar to about 100 millibar. The sample can be exposed to such forces for any suitable amount of time. Particularly exclusive aspects of the invention comprise a mild vacuum pressure, such as between about 1 millibar and about 500 millibar, such as about 1 to 300 millibar, about 1 to 250 millibar, about 1 to 200 millibar or about from 2 to 200, 2 to 150, 2 to 100, 3 to 200, 3 to 250, 3 to 100, 5 to 250, 5 to 200, 5 to 100, 1 to 50, 2 to 50, 3 to 50 or 550 millibar of pressure for a period of less than 15 minutes, such as less than 10 minutes, such as less than about 9 minutes, less than about 8.5 minutes, less than about 8 minutes, less than about 7 minutes , less than about 5 minutes or even less than about 3 minutes, less than about 2 minutes or less than about 1.5 minutes or less than about 1 minute, such as about 0.25 to 15 minutes, about 0.33 to 12 minutes, about 0.5 to 12 minutes, about 0.33 to 10 minutes, about 0.33 to 11 minutes, about 0.5 to 11
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103/164 minutes, about 0.5 to 10 minutes, about 0.65 to about 11 minutes, about 0.65 to 10 minutes, about 0.5 to 7.5 minutes, about 0.33 7 minutes, about 0.5 to 5 minutes, about 0.33 to 5 minutes, about 0.75 to 7.5 minutes, about 0.75 to 5 minutes, or about 1 to 10 minutes, as like about 1.5 to 9.5 minutes, like about 2 to 9 minutes, like about 4 to 8.5 minutes, like about 5 to 8.5 minutes, or like about 6 to 8 ,5 minutes. The sample can also or alternatively be exposed to other forces, such as subjecting the sample to a crushing force, optionally in addition to one or more other forces, such as vacuum pressure, vibration energy or radiation energy, such as such as laser excitation, or a combination of any or all of them. The application of crushing forces can provide a fracturing aspect to the method, in which measures, such as ductility and / or hardness, are determined (for example, by crushing a flexible container comprising the sample), as described above. Volatile substances can be analyzed by any suitable means, typically by means comprising spectrometric mass analysis. In some respects, the method may comprise removing potentially interfering gases from the media, but in other respects, such a step is not practiced or is not necessary. In some cases, these methods are characterized by not heating the samples to temperatures greater than 100Ό when carrying out the method. In some respects, the method comprises collecting and sealing samples in the wells versus samples loaded in the laboratory. Such methods may include collecting and analyzing samples in close proximity to the well site. For example, the method may comprise performing the method within 60.96 meters (200 feet), such as within 30.48 meters (100 feet), 22.86 meters (75 feet) or 15.24 meters (50 feet) from where the samples are distributed to
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104/164 surface. The method may comprise transferring the samples by conveyor belt, pneumatic tube system or other system to a site, or even distribution by drone, to a laboratory for analysis, which can be located within 804.67 meters (0.5 miles) , such as within 402.34 meters (0.25 miles) or even 160.93 meters (0.1 miles) from the pit site.
[180] In another aspect, these methods are performed in relation to an active well, such as a piece that is under active drilling, so that the method can provide real-time or near real-time analysis of samples. For example, in some ways, the difference or delay time between the drilling site (drill bit location) and the sample site where the most recent analysis is performed is about 15.24 meters (50 feet), such as less than about 12.19 meters (40 feet), less than about 9.14 meters (30 feet), less than about 6.1 meters (20 feet) or less than about 3.05 meters ( 10 feet), 2.13 meters (7 feet), 1.52 meters (5 feet) or even less than about 0.3 meters (1 foot). Such methods may comprise actually taking samples from the well line and, for example, transmitting the data connected with the hardness of the samples, such as by crushing or squeezing samples collected in the well, to the surface through optical fibers, vibratory signaling from the line. well or similar. In other cases, the analysis of samples at the well surface may also provide an inexpensive alternative and / or a complement to the gamma ray mapping that is currently performed and a faster analysis than currently performed X-ray diffraction methods and may be used as a means of mapping a material (formation, region) and directing drilling / fracturing operations. The data collected from such operations can be digitized or otherwise transmitted as data through a computer system and then used to target or provide
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105/164 automatically information to human operators through, for example, a graphical user interface, which can assist in the direction of well site operations. In some respects, the method is performed with a well that has increased mud flow compared to current mud flow rates in order to provide real-time analysis through cuts, which can be particularly useful when analyzing cuts in time Real is made with cuts cut to the surface.
[181] The data collected in the analysis can be any type of data, but, as described in this document, will favorably include analysis of acetic acid, formic acid and / or oil-saturated water associated with the sample. The analysis also or alternatively may include measuring the amount of methane, carbon dioxide and / or carbon monoxide that is released from the samples or released from a trap of volatile compound.
[182] Given the variable nature of materials to be analyzed, the scale of the data that is analyzed in methods that are related to the analysis of volatile compounds may vary. This may be true even for a particular type of data, as the conditions under which the sample is collected may vary. For example, in relation to the cuts, the age of the cut, the condition of the cut and its storage, and the nature of the materials contained in the cut can influence the scale. Thus, in one aspect, the method may comprise evaluating the material through routine experimentation or by guidance provided through standards or similar means, such as machine calibration that is programmed based on variables (for example, oil wells known to similar nature can be mapped and used as a calibration for similar wells), to assess the correct measurement scale for plotting or otherwise analyzing the data, as exemplified in the examples provided
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106/164 below. The method typically then comprises looking for indication of the presence or absence of one or more of the compounds of interest. When multiple samples from multiple locations are taken, typically a map or plot will be generated, again as exemplified in the examples. In such a case, the method will typically comprise patterns of searching manually or automatically in the data in the selected scale (or scales) that will indicate changes and anomalies or “hits. In some cases, the change in the amount of a target substance on a scale will be from a level of “0 or almost 0, or lack detection, to the detection of any value above 0. As another example, for example, in which oil as a percentage of total rock value is used as a measurement, in some contexts (for example, rocks with a porosity of around 8%), a measurement of at least 2% could be considered “high oil value, and low values could be set at 0.1% or lower. By plotting the data, clear patterns can be seen. Often, a measurement of about 15% of the scale or more (for example, about 25%, about 30%, about 40%, about 50% or more) could be considered a “hit. The analytical aspect of a volatile facet of the invention may also comprise analysis of two or more types of data, such as permeability at one depth and non-permeability at another, for example, to identify oil-trapped zones that can be very beneficial. Also and alternatively, several measurements, such as oil-saturated water, can be combined with other measurements, such as formic acid, acetic acid and the like, so that it is possible to measure the oil production zone and the formations around the zone of production that are in fluid communication with the production, as evidenced by formic acid, acetic acid and water saturated with oil. The combination of permeability and other information,
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107/164 specifically when combined with other data from conventional media, it can provide maps that identify one or more production zones in a material / region. The use of data including other hydrocarbons may further explain the nature of the oil, such as whether there is heavier oil or lighter oil present (or otherwise if the oil and / or gas deposits are of a similar or different nature and / or if the gas can be considered to assist in transporting oil to the surface, etc.), and relative oil deposit locations, if there is a “seal (low permeability region) around the oil deposit and / or oil deposit locations in relation to water and other oil and / or water pockets in the material / region. Such data can assist in determining whether or not different production zones can be obtained together or separately and under what conditions the production zones can be obtained. Thus, for example, the analysis of such data can reveal whether or not an oil or gas deposit is compartmentalized in relation to other oil deposits in the material / region.
[183] As determined above, the various disclosures related to the methods of the invention can be readily applied to devices and systems of the invention, which are also exemplified in the examples provided below. Thus, in another facet, the invention provides devices that comprise (a) a container or chamber for receiving and isolating samples of a material and (b) a detection component capable of detecting the quantity of one or more target volatile substances released from the sample , wherein the substance comprises carbon monoxide, acetic acid, formic acid, or a combination thereof, optionally in combination with hydrocarbons, inorganic gases or a combination thereof. In yet another facet, the invention provides a device that comprises a crushable component or material
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108/164 which may contain samples, which, when crushed, provide information regarding the strength of the sample (and thus the material) and a system comprising such a device and means for crushing the device (as well as, optionally, means for measure information, store information, relate information, etc.). In yet another facet, the invention provides devices and systems that are capable of both analyzes.
[184] In relation to devices that are capable of volatile substance analysis, a device of the invention typically comprises an energy input component that promotes the release of volatile substances from the sample. The energy input component typically is or comprises (a) a pressure generating device or system, (b) a device or system that promotes the release of volatile substances through mechanical forces, thermal forces, or both, or a combination of (a) and (b). Often, the device or system will comprise means (component, system or the like) to isolate volatile substances released from the sample sample, the environment and / or other components of the system or device, such as one or more operable valves. Devices and systems will often include a trap, which can be non-selective or selective trapping, or comprise both types of trapping. The trap can be, for example, the trap of liquid nitrogen, which is capable of capturing volatile products, condensable gases, released from samples, such as cuts. The dimensions of such devices are described elsewhere in this document, as they are suitable materials from which such devices can be manufactured.
[185] Devices for analyzing volatile compounds typically include means for measuring volatile substances. This may include, for example, a carbon monoxide detector or another type of detector
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109/164 chemical and, also or alternatively, a specific detection system, such as a mass spectrometer, examples of which are provided elsewhere in this document. When advantageous, the analytical parts of the system can be optionally isolable from other parts of the system, such as to ensure proper operation and / or to prevent false signal events. The device / system of the invention may further comprise a programmable or data logic component for collecting data, relating data, storing data, and the like, which may include alarms, automatic device means (such as means for directionally controlling a perforation) ) and / or a graphical user interface. The operation of the device / system components can be similarly automated and / or placed under the control of a programmable unit or computer system.
[186] In another aspect, the invention provides systems or devices for chemical analysis of volatile compounds in a sample of a material comprising (a) a cryogenic trap that can be cooled and maintained at temperatures that are capable of capturing target volatile substances when such substances are in fluid communication with the trap (for example, temperatures of about -100 degrees C or colder, such as about -110, about -120, about -130 degrees C or less) (for example, the device / system will typically include a cooling component or cooling medium that is capable of selectively cooling cryogenic entrapment, which in practice may be one, two or more separate entrapments); (b) optionally, but typically, a component or system for selectively heating cryogenic trapping in a controllable manner, (c) one or more devices or systems for applying one or more forces to the samples to which the system is applied, such as a vacuum system, preferably with the ability to apply multiple levels of vacuum pressure to the sample
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110/164 and, in preferred aspects, the ability to apply relatively low / gentle vacuum to a sample, such as about 25 to 150 millibar pressure (for example, about 60 to 120 millibar pressure) to a sample, ( d) components to contain volatile substances and keep substances isolated from the environment, such as a housing, (e) components to selectively isolate sample entrapment, so that volatile compounds can be exposed to entrapment only after cooling to a desired temperature, (f) an optional component for capturing volatile substances that will not condense on trapping, which is typically selectively isolated from other substances so that non-condensable materials can be analyzed separately from materials that condense or otherwise bond entrapment and are subsequently released from imprisonment and (g) a device for analyzing at least some of the substances volatiles released from trapping, such as a mass spectrometry device, optionally with means / components to selectively allow the volatile substances to access the analytical device (eg one or more selectively open valves) and (h) means or components for cause the transport of at least some of the volatile substances captured in the confined system. Such a system may also or alternatively further comprise (i) a component or means for evacuating any non-condensable gases out of the cryogenic trap, as and if necessary, without releasing any condensable volatile products from the cryogenic trap if the analytical method require high vacuum, such as a selectively operable pumping system. Systems that have means / components for analyzing non-condensable gases / materials may further comprise means for capturing a defined volume of such non-condensing materials, such as
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111/164 as selectively operable vacuums that can act on such materials and / or components / means to selectively expose such materials to the analytical part of the system and often means / components to transport such materials to the set of analytical components of the system / device.
[187] As described above, a cryogenic trap can be generated by contacting a suitable medium with a cryogenic substance, such as liquid nitrogen, liquid argon, liquid oxygen, liquid air, liquid helium, dry ice, a dry paste of dry gel , normal ice, a normal ice water ice slurry in fresh water, a normal water ice ice slurry in a saline brine or any other natural cooling substance capable of reaching the minimum temperature required to freeze the substance (or substances) of interest in cryogenic trapping. A cryogenic state can also and alternatively be achieved with refrigeration or mechanical cooling, as can be achieved with a Kelvinator device. The Kelvinator device or other cryogenic device must be able to reach the minimum temperature required to freeze the substance (or substances) of interest in cryogenic trapping.
[188] A cryogenic trap component can have any suitable configuration. In an exemplary embodiment, the trapping will be configured in such a way that the cooling of the cryogenic trapping device occurs outside a cryogenic chamber and volatile substances adhere to the inside of the cryogenic chamber. Alternatively, a trap can be provided in which the cooling of the cryogenic device occurs inside the cryogenic chamber and volatile substances adhere to the outside of the cryogenic chamber.
[189] In one respect, cryogenic entrapment comprises
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112/164 one or more materials that are suitable for cryogenic trapping, which are typically selected from materials that comprise one or more suitable metals, such as aluminum, copper, gold, silver, platinum, palladium, stainless steel, brass, bronze, nickel , cobalt or any other suitable metal, including alloys and / or any suitable combinations of such materials. A trap, also or alternatively, can be composed of non-metallic material, optionally a non-metallic material that forms a substrate for trapping volatile substances, such as, for example, carbon fibers, peek, natural or industrial diamonds or diamond films , glass, ceramics, or any other suitable non-metallic substance or combination of such substances, alone or in additional combination with one or more metallic substances. The imprisonment may have any suitable shape or configuration, including, for example, a shape selected from a cylindrical shape, a u-shaped, polygonal, spherical, funnel-shaped, ribbed, helical and / or botryoidal shape or any other suitable shape.
[190] A system or device comprising a component or cryogenic system according to such aspects of the invention can be configured to analyze any type of volatile compounds or sample (or samples) associated with volatile compound. While the description in this document places a significant focus on extracting volatile substances from geological materials, especially from oil and gas well materials and, in particular, from oil and gas well cuts, the methods of the invention can be performed, as already determined in this document, with other types of samples and, in another facet of the invention, they can still be practiced with volatile fluids that are independent of any type of solid sample. For example, in one aspect, one or more methods of product analysis
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113/164 volatile of the invention, such as those described above, are also or alternatively applied to a liquid, such as one or more drilling muds. In another aspect, such a method or set of methods is also or alternatively applied to a gaseous substance (for example, a substance that is substantial, predominant or entirely a gaseous state under normal atmospheric conditions). In such aspects of the invention, the method of the invention may comprise filling a container or component of the system with the gas to be analyzed and allowing the gas to make contact with a trap, such as a trap of liquid nitrogen, and then subjecting gases released from entrapment to analysis, such as by mass spectrometry. When gas is supplied in a container, such as a bottle, the method may include the step of filling the bottle, optionally sealing the bottle, and optionally forming a flow of fluids in a sealed manner between the bottle and the system so that volatile substances in the gas are not lost due to escape or reaction. Alternatively, gas can be captured in a device, such as a syringe, and introduced into a system, for example, a vacuum system, by passing a needle through a septum, and thus emptying some, most, all or essentially all the components of the syringe at an entry into the system and, eventually, immediately or almost immediately afterwards at an entry to a trap and, subsequently, an analytical device (or where a trap is not used, directly to a device analytical according to such aspects of the invention). Yet another alternative facet of the invention provides a method in which a gas containing quantities of volatile products, such as very low / residual amounts of volatile products in the gas, is to allow condensation of the gaseous volatiles in a trap, such as a trap of
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114/164 liquid nitrogen, over a relatively longer period of time, to allow the accumulation of even residual amounts of volatile products in trapping. Such a process could be used to detect extremely small amounts of volatile products associated with explosives in the air or residual amounts of hydrocarbons and / or organic acids in the air associated with natural oil spills or other relevant residual chemicals, such as environmental contaminants. Thus, such an instrument, and even many of the other devices and systems described in this document, can be usefully installed as a mobile unit in a car, truck, plane, boat or even a rocket. A system with multiple liquid nitrogen entrapments could provide continuous monitoring while one entrapment was extracting a sample to analyze, another entrapment could analyze the previously entrapped sample.
[191] The systems and devices of the invention will typically comprise a device or means for introducing volatile products from a sample into the system in an isolated manner. In an advantageous aspect, as exemplified elsewhere in this document, the system includes a set of components and / or means for introducing volatile substances to the device / system by means of syringe or needle injection, which often advantageously comprises a portion of perforates, penetrates or otherwise crosses a septum, which will typically be associated with a sample container in which the samples can preferably be contained in a sealed state, so that the loss of volatile substances is minimized ( for example, the system may comprise one or more samples that are hermetically sealed to a cryogenic trap entry). The system will typically comprise a set of components / means for generating gas flow over the
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115/164 cryogenic trapping, such as pumps and the like. The system can also optionally comprise gas sources, such as air or other gases, which can assist the flow of volatile substances in the system / device.
[192] An analytical device for the evaluation of volatile compounds according to such aspects of the invention typically comprises a mass spectrometer, but it can also or alternatively comprise one or more additional analytical devices, including, for example, a gas chromatograph; an infrared spectrometer; a Raman spectrometer; or any combination thereof, including multiples of the device of the same type (for example, multiple mass spectrometers); or any other suitable analytical medium and / or combination of analytical mediums. As described elsewhere, the device / system will often include programmable logic media / components that can automatically put the operation of the device under control and capture, record and / or transmit and / or display data obtained from the performance of the method in the form digital, printed or other known forms.
[193] The combination of the components described above in devices and systems provides several additional or alternative innovative aspects of the invention. Thus, for example, the invention provides an innovative and useful device comprising (a) a cryogenic trapping device / component that is in fluid communication, typically selective fluid communication, with one or more mass spectrometers, usually in a mode configuration that allows the release of material from the cryogenic device / component to the mass spectrometer component. Such a device may comprise means / components for material flow through the system and means / components for selectively heating the
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116/164 cryogenic trapping.
[194] In another aspect, the invention provides devices and systems that comprise (a) a non-selective trap that captures volatile substances in a sample of materials, (b) a housing or other housing that prevents the loss of volatile substances in materials in the system (at least in significant quantities, such as keeping at least 90%, at least 95%, at least 98% or even 99% or more of the volatile substances associated with the sample once the sample is placed in a trapped manner) communication with the system), (c) an analytical device that can detect one or more primary and / or secondary compounds that are associated with target materials, such as oil and / or natural gas, (d) components or means for transporting volatile substances entrapment and (e) components or means for selectively releasing materials from entrapment in a manner that allows the determination of the presence or absence of at least one, preferably at least two and typically 3, 4, 5 or more (e.g., at least 6, at least 7, at least 8 or even 10 or more) substances in the system. Typically, such a system will further comprise one or more forces that can be applied to the system to promote the release of volatile substances, such as different pressures, which may reveal additional information elements regarding the substances, such as sample permeability, and / or will comprise means / components to cause chemical reactions of volatile substances, for example, by producing water in the system from one or more trapped substances. The systems may also include means / components for selectively crushing / squeezing the samples and providing a measurement related to them so that the compressibility and related ductility / hardness of the sample can also or alternatively be provided. Containers of
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117/164 samples provided by the invention are also useful and innovative devices in their own right. Thus, for example, the invention provides a sample container that comprises a selectively perforable section, a housing that is capable of containing sample materials, such as cuts associated with an oil well, and that is also at least substantially impermeable to the release of volatile substances and, optionally, a crushable selection or component that allows the application of crushing / clamping forces on the container, in a known manner, resulting in a measurable amount of compression of the container that provides relative information on the hardness / ductility of materials in the container and also optionally promotes the release of volatile substances. Optionally and frequently, such a container is configured to be in sealed fluid communication with one of the devices of the invention.
EXEMPLIFICATIVE MODALITIES AND APPLICATIONS OF THE INVENTION [195] The following examples further illustrate various aspects of the invention, but should not be construed, in any way, as limiting the scope of the claims or the rest of the disclosure provided herein.
EXAMPLE 1 [196] This example provides a description of an exemplary device / system according to certain aspects of the invention and which is also suitable for application of several of the methods of the invention described in the present document. An overview of the exemplary device is provided in the following figure (Figure 1).
[197] Regarding the device / system shown above, n ² 1 represents a first sample container, as described elsewhere in this document. The first sample container n ² 1
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118/164 contains the sample of the material, such as cuts taken from an oil well. Sample container No. ² in the case of the system shown is sealed and made of impermeable material. The upper portion of any sample container used in the system, such as the first sample container n ² 1, is penetrable by needle n ² 2, which provides a passage and means for transferring gases released from the sample into the rest of the system, immediately after penetration and / or after generation through the application of one or more forces acting on the sample.
[198] A second sample container n ² 2 and a third sample container n ² 3 are also shown, reflecting the fact that the systems of the invention are often run with numerous samples in a given round or load (for example, by at least 5, at least 10, at least 15, at least 20, at least 25, at least 30, at least 35, at least 50 or more samples). In the case of the represented system, a sample carousel, n ² 4 is provided, in which several samples to be analyzed in the particular round are loaded. Automation types other than a carousel could also be used, such as a cartridge that holds a plurality of samples in a vertical or horizontal profile (not shown), or at any angle between vertical and horizontal, which can distribute samples in any position suitable for volatile product analysis (also not shown). Samples loaded on a particular load or round are typically related to each other, such as samples taken from a particular well site and kept under particular conditions, but this is not necessarily always the case. In some embodiments of the invention, carousel n ² 4 is automated to function once the analysis on a particular sample is completed, this will often be controlled by a programmable computer that is connected to the
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119/164 system and in control over various functions that operate in the system (and thus the system components). Thus, for example, when the analysis has been completely performed on the first sample container n ² 1, the carousel can automatically rotate, positioning the second sample container n ² 3 in position, so that a penetrable portion of this sample container can be penetrated, such as by needle No. ² 8. Loading and transfer need not be in the form of a circular carousel, but could, for example, be in the form of a conveyor belt or any other suitable sorting mechanism. The penetration of the sample containers by the needle can also be under automatic operation or, more typically, it is subjected to operation by robot or computer once certain conditions have been met (and subjected to manual control). The sample containers shown here comprise side walls that are made of a robust, but crushable / deformable material, such as brass, of a relatively fixed thickness.
[199] The system depicted also comprises a plunger No. ² 5 which is manufactured from a material that is suitably composed and configured so that it can distribute an impact on the crushable side wall or other modifiable portion of the container. For example, the piston n ² 5 can be manufactured from a stronger metal such as steel, which can be repeatedly used to crush the sidewall of the container and thereby dispense a crushing strength of any sample materials contained therein , such as oil well cuts. The piston n ² 5 is typically connected to pistons n ² 6, which can be air pistons or another suitable type of piston (or pistons). The pistons No. ² and the piston No. ² typically form an apparatus or system for clamping or crushing together, as shown. The pistons No. ² 6 can be used to drive the plunger
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120/164 η ² 5 in the crushable portion of the sample container, for example, n ² 1, by means of a user command, under some automatic condition, and / or when directed by a computerized control system. The plunger is typically driven by the piston or other actuating mechanism (for example, a powerful spring) in the container with a force that is suitable for crushing a portion of the container and distributing enough force to crush the sample material, thereby releasing volatile compounds and assisting the release of such volatile compounds in combination with the application of other forces or energies, such as vacuum pressure. The system typically comprises an anvil, n ² 7, which assists in crushing the n ² 1 container, providing a hard surface against which the container is pressed when the plunger n ² 5 is brought into contact with the n ² 1 container by application of pistons n ² 6.
[200] Needle n ² 8 is also typically associated with a set of needles, comprising a connection block n ² 9, which, as shown, is connected to a leveling screw, n ² 10, which can raise or lower the needle in order to cause the needle n ² 8 to pierce a seal or other perforable portion of the container n ² 1 when engaged (alternative devices or means to raise and / or lower the needle could also or alternatively be used). The coupling can be performed manually, automatically and / or by computer program control. The connector block 9 n ² comprises a channel portion in which the gas passes from the sample container ² n 1 and n ² through the needle 8 can flow. In the embodiment shown, the channel portion of the n ² 9 connector block is in communication with a selectively lockable (lockable / open) right angle valve n ² 11, which controls the flow of gases from the sample container / needle / connector block to the other portions of the system. “In communication, in the context of the represented device,
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121/164 means that gas can flow between chambers, elements or devices that are described as being “in communication. The first right angle valve, No. ² 11, as with other components, can be opened and closed manually, automatically and / or under the control of a computer, fixed to the system, in order to practice the methods of the invention. In some cases, for example, the valve is closed to allow controlled release of gases from sample container n ² 1 to the rest of the system. The control provided by the inclusion of this first right-angle valve, and other valve controls in the represented system, can, for example, allow different “runs of the system in a single sample, under different conditions, such as under the application of different pressure of vacuum in the sample. Other types of valves, such as ball valves, in-line valves or any other type of valve that can operate satisfactorily in a vacuum system (not shown), could be used instead of right angle valves as exemplified here and described anywhere in this disclosure.
[201] Two other right angle valves (n ² 12 en ² 13) are connected to and are in communication with the first right angle valve, n ² 11, and, respectively, control the flow of dry nitrogen in the system and the flow sample gas in container # ² 1 to the liquid nitrogen trap container. Other purge gases, such as dry air, argon, oxygen, helium and others can also be used alternatively as purge gas instead of dry nitrogen. Similarly, other cryogenic fluids, such as liquid oxygen, liquid argon, liquid helium and any other suitable cooling fluids could also or alternatively be used as the cooling medium instead of liquid nitrogen exemplified here and described elsewhere in this document.
[202] The outer right angle valve is connected to a
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122/164 flexible vacuum hose, n ² 14, which accommodates the up and down movement of the needle assembly that rises or falls in several sample containers (n ² 1, n ² 2, n ² 3) on the carousel (n ² 4). Vacuum hose No. ² 14 is also used to allow the gas flow to create a vacuum pressure and also to allow sample gases to pass through the system. A pressure gauge n ² 15 provides the operator with pressure conditions in the system and thus provides a check on whether the system is operating as expected, which is important to ensure the validity of experiments and analyzes in the system (other means / devices to measure pressure also or alternatively could be used). A fourth right-angle valve # 16 controls access to a # ² diffusion pump 16a, (which is typically connected directly, as shown), which is used to expel gases from the system (alternative means and devices to pump or alternatively could included in such a system). A fifth right angle valve, No. ² 17, provides a second control of entry into the liquid nitrogen trap container. As already mentioned, all of these valves are controllable, and the control over the valves can be configured to operate in any suitable manner, in order to carry out the various methods of the invention.
[203] A relatively long first tube, n ² 18, which is typically comprised of aluminum or a similar material, provides communication between the right angle valve n ² 17 and the liquid nitrogen-based cooling chamber, n ² 20, which also acts as the exterior of the liquid nitrogen trapping components of the system. Along tube n ² 18, one or more heaters, n ² 19a and ² 19b, can be positioned, which allows the application of heat, in a relatively predictable way, to the system, which will assist in the release of frozen gases to the trapping of Liquid nitrogen. The
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123/164 heaters can be any suitable type of heater, including units that radiate heat, leftover hot air or that heat the pipe by other suitable means. Typically, heaters (n ² 19a and ² 19b) are placed at the ends of the first tube n ² 18.
[204] The liquid nitrogen-based cooling chamber n ² 20 is the exterior of the liquid nitrogen trapping freezing region. Here, the gas can come into contact with the system's liquid nitrogen-cooled component set and freeze on entrapment. The flow of liquid nitrogen is controlled by a liquid nitrogen valve, n ² 21. A thermocouple, n ² 22, provides the user with the ability to monitor the system temperature and, optionally, can be configured to send information to a associated computer, which can control certain system functions. The trapping of liquid nitrogen has its own temperature controller, n ² 23, which helps in controlling the application of liquid nitrogen. A sixth right angle valve, No. ² 24, is positioned at the outlet of the liquid nitrogen trapping region and controls the flow of trapped gases to the rest of the system. A specialized right-angle valve, the release valve, n ² 26, is a pinhole bypass to analyze the gas that is released by heating the liquid nitrogen trap due to the operation of the heaters, n ² 19a and ² 19b. As described, in general, above, liquid nitrogen is applied to this region of the system, lowering the temperature to a point where the volatile compounds contained in the sample can freeze this trapping region. The application of heaters, then, allows the release of frozen gases from the region to the rest of the system, including the mass spectrometer, n ² 31.
[205] A pinhole device, No. ² 25, is configured to
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124/164 regulating the flow of non-condensable gases from the non-condensable gas trap, n ² 27, into the mass spectrometer, n ² 31. The non-condensable gas trap, n ² 27, is configured to collect gases that will not bind trapping liquid nitrogen. The non-condensable gas trap # ² 27 comprises a right-angle valve, which allows the selective opening of this part of the device, so that the gases released from the heating of the liquid nitrogen trap are kept separate from the non-condensing gases.
[206] Diffusion pumps, n ² 29 and ² 33, which can be supported by thinning pumps, provide flow and pressure control in the system and are controlled by the respective valves, n ² 28 and ² 32. Often, any other type or types of suitable high-vacuum pump (or pumps), such as turbomolecular or cryogenic pumps or any other types of high-vacuum pumps may be used instead of where diffusion pumps are quoted anywhere in this application. Control via manual operation or computer system provides different amounts of pressure (positive or negative) in all or parts of the system through the operation of these pumps. As discussed above, in operation, several rounds of the system can be performed even on a single sample “by pulling the sample through the application of different vacuum pressure conditions, thus releasing different amounts of gases, thus forming different aliquots at from a single sample.
[207] Access to the mass spectrometer, n ² 31, is controlled by a mass spectrometer valve, n ² 30. Any suitable mass spectrometer can be used in the system, and many are discussed above. Mass spectrometer n ² 31 is configured to send information to a computerized system (not shown), typically via an output connector
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125/164 (shown as wires connected to mass spectrometer n ² 31), indicating the presence of target compounds of interest, such as hydrocarbons, inorganic gases, carbonic acid, acetic acid or other organic acid, or the products' early decomposition products themselves, such as water or carbon monoxide.
EXAMPLE 2 [208] This example demonstrates the use of methods of the invention to determine oil and water saturation in a formation based on the analysis of sections taken from an oil well, as well as permeability analysis obtained by analyzing a series of cuts taken from the well.
[209] Thirty samples of unsealed cuts taken from different depths in an oil well that were stored in unsealed containers for a period of approximately three months under summer warehouse conditions (about 37.78 to 54.44 degrees C (100 to 130 degrees F) of estimated maximum daily temperature) were subjected to analysis using a device as described in Example 1 to provide information related to the permeability of samples taken from different depths in the oil well, based on the release of target substances. The cuts were subjected to two rounds of the system, forming two aliquots, based on the application of pressure conditions of 50 millibar and 5 millibar, respectively.
[210] The right column of Figure 2, shown below, represents an actual plot of the relative permeability of these samples, provided by two conventional permeability methods (for example, the downward pointing triangles n ² 1 are measurements of wall core permeability. lateral curves, curve n ² 2 represents permeability assessments carried out using conventional well profiling methods) and by application of the
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126/164 method of the invention (upward pointing triangles, n ² 3), as applied to sections of an oil well site. These data represent one of the first times that the permeability information of a site was obtained from oil well cuts, and the data show that oil well cuts can provide permeability information that correlates with data obtained from significantly more traditional methods. The permeability data were plotted in milidarcy or in relative proportion to other permeability measurements using conventional techniques.
[211] Other information included in Figure 2 is a plot of mud profiling data (gas chromatography data), in the second column on the left, indicating the presence of C1-C5 hydrocarbons in mud obtained from the respective plotted depths of the well (y-axis).
[212] The intermediate column provides Sw plots obtained from various methods (the continuous line, n ² 4, represents data from conventional well profiling and the points, n ² 5, represents data taken from sidewall witnessing methods) . The triangles, n ² 6, are data obtained by the method of the invention that are applied directly to the well cuts. The results demonstrate a strong correlation in terms of S _w , here being obtained from cuts and also from more conventional and often more expensive methods. This is another innovative aspect of the invention, obtaining both permeability and Sw data from cuts in a single round and providing a comparative analysis of such data, for different depths of a well, against other conventional methods for evaluating a well site.
[213] Other information provided in Figure 2 includes the mud profile resistivity curve, oil staining data in
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127/164 cuts, gauge data (measuring drillhole sizes, red dashed lines) and conventional gamma ray data (which provides information on the type of material at the site - such as shale versus sandstone, carbonate, etc.) ( plots in the first column on the left). The correlation of this information was used to identify the zones, which are indicative of the presence of oil, as indicated by the leftmost vertical bar, n ² 7. The water segment below the oil production zone is indicated by the vertical bar below the left, n ² 8.
[214] In this data, conventional resistivity data fails to convincingly identify the presence of oil that could be detected by the method of the invention. This may be due to the inability of the resistivity data to differentiate between oil and gas, due to the fact that both compounds are not conductive. This is an advantage of the methods of the invention exemplified by this example. The area of the most abundant oil fluid inclusions was the water segment n ² 8, not the oil production zone n ² 7. Thus, the use of the fluid inclusion methods described earlier in this well also failed to identify areas of oil oil production, which could be identified by the cutting methods of the invention, thus also reflecting a benefit of the method of the invention.
EXAMPLE 3 [215] This example demonstrates the identification of an oil production zone, by applying the method of the invention to oil well cuts, which were taken from a section of an oil well that is not being explored based on in the application of pre-existing analytical methods.
[216] Five hundred and eighteen cuts taken from an oil well site, sealed in the well, were used in this analysis. Three aliquots were obtained from each cut, using similar pressure conditions
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128/164 to those described in Example 2, plus an aliquot after intense sample dehydration. The permeability measures were obtained by the difference between aliquots 2 and aliquot 1 for each sample of cuts, n ² 1. The analysis data were plotted and the real plot of these data is shown in Figure 3.
[217] Numerous additional data points were also obtained and are reflected in Figure 3, such as formic acid n ² 2, acetic acid n ² 3, water saturated with oil n ² 4, presence of C5-C10 paraffins n ² 5, C6-C10 naphthenes n ² 6, C6-C8 aromatics n ² 7 and total oil n ² 8. The components of methane gas n ² 9, ethane plus propane plus butanes n ² 10 and Total Gas n ² 11 are also plotted, as is the sum of oil and gas n ² 12. The measurements that indicate oil and gas were obtained by adding the results of all three rates. The quality of the oil and gas product is indicated by the C8 / (C5 + C6 + C7 + C8) curve that helps to differentiate heavier oil that plots on the right versus lighter oil and gas that plot on the left. The GOR curve (gas to oil ratio) n ² 14 helps to determine gas-prone versus oil-prone areas. The paraffin curve / (paraffins + naphthenes) n ² 15 and the aromatics curve / (aromatics + naphthenes) n ² 16 are used to assess the quality of the oil and to distinguish several different oils from each other.
[218] These data reflect the identification of a separate oil production zone. The low permeability region n ² 17 in the graph reflects a poorly permeable area overlying an accumulation. Below this poorly permeable zone (a zone of low permeability, generally less than 9.87 x 10 ^'12 m ² (10 milidarcies) and typically below about 0.98 x 10' ¹² m ² (1 milidarcy) ( a poorly permeable zone that covers the production, preventing its migration in the material, can be considered a “seal” (these terms are also subject to general understanding in the technique), two zones containing oil were identified through the evaluation of the various
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129/164 basic data points. The upper zone n ² 18 was overlooked by previously applied methods, but it was identified through analysis of oil well cuts, using the methods of the invention, while an area of real oil production n ² 19 was confirmed by the application of the various methods of the invention in oil well cuts.
[219] A simplistic interpretation of these data is reflected in Figure 3b, which specifically reflects and focuses on key signals in the permeability and oil-saturated water data that characterize the geological (material) formation studied in this example. Specifically, the permeability data reveal a little permeable zone, n ² 17, with little permeability, above a non-target zone identified by water saturated with oil according to the method of the invention employed in this Example, n ² 18, as well as the confirmation of an identified area using other conventional methods, n ² 19, through analysis of water saturated with oil.
[220] The concept of “water saturated with oil was developed as part of the invention described in this document. “Water saturated with oil refers to water that has chemical indications of fluid communication with oil. Specifically, samples indicative of containing oil-saturated water refer to those samples that show relatively high amounts of formic acid, acetic acid, carbonic acid and / or bicarbonate indicator compounds, often from the presence of their broken indicator compounds, especially carbon monoxide and / or water, or from a combination of detection of such primary and secondary indicators. Any of these conditions can be combined, such as, for example, the methods of the invention may include determining the amount of water, one or more other inorganic gases (for example, one or more among hydrogen, helium, nitrogen, argon, oxygen, hydrogen sulfide, carbonyl sulfide, sodium disulfide
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130/164 carbon and / or sulfur dioxide), carbon monoxide, carbon dioxide, carbonic acid, acetic acid, formic acid, methane or other C1-C5 hydrocarbons, and / or bicarbonate that is associated with / released from a sample as a means of determining whether it is associated with target substances, such as oil and / or natural gas. The analysis conditions typically need to be at least partially controlled in order for the water to provide an indication of such material and thus communication with oil in a geological formation. Thus, in relation to a device / system, such as that exemplified in Figure 1, and described above, water is advantageously released from the trapping of liquid nitrogen at a temperature colder than the water sublimation temperatures usual in the device / system, usually about 55 degrees centigrade. Part of this water can also be detected at very low liquid nitrogen trapping temperatures, such as around 140 degrees Fahrenheit. Water with high amounts of indicator compounds can be considered water saturated with oil, while water without these indicator compounds is not water saturated with oil. This characterization of water in a formation cannot be performed with conventional methods, especially in areas with very high water saturation, where conventional well profiles essentially do not provide information as to whether this specific water is in communication or not with accumulations of oil and / or commercially viable gas. The determination of the presence of the indicator compounds by the analytical methods of the invention provided here allows this important distinction to be made. This tool can also be applied to wells that do not find commercially viable amounts of oil and / or gas, that is, dry holes, to determine whether such large amounts of commercially viable oil and gas occur near the dry well site or do not. These analyzes
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131/164 could also be carried out at the well site, and indicated oil and gas zones nearby could be targeted with directional drilling wells drilled from the initial pilot well at the fraction of the cost of drilling another well to explore the nearby drilling zone at a later date.
[221] This Example shows that data derived from cuts, such as permeability and water saturated with oil, can be used to determine the presence of oil and also to determine permeability and discrete geological zones containing oil, even those lost by other conventional methods .
EXAMPLE 4 [222] An analysis was performed as described in Examples 2 and 3 on 139 cuts that were sealed in the well or in the deepest section of the vertical pilot oil well described in Example 3, other samples were taken from a perforated side line as a directional drilling of the pilot well after assessing the pilot hole to locate the deep production zone. Three aliquots were analyzed for each sample under the pressure conditions described above in Example 3. The results of water saturated with oil are shown in Figure 4a (element identified n ² 1).
[223] The oil-saturated water anomaly in the vertical pilot well reveals an oil-rich production zone n ² 2, which then became the target for drilling and fracturing the side directional drilling. High water saturations are indicated above n ² 3 and below n ² 4 the oil production zone n ² 2. To be able to use this information to assist in deciding how deep to drill and set a directional drilling to the side of a pilot hole requires very fast analytical and interpretative response time. Usually, the interpretation needs to be distributed within 24 hours of the vertical pilot well reaching its full depth. Samples are often expressed
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132/164 by air back to the lab or sent immediately by car if close enough, once or twice a day, so that analyzes can track the drilling of the can as much as possible.
[224] Data from water saturated with oil from the side directional drilling n ² 5 show that the side was in the oil production area n ² 2 penetrated by the vertical pilot well for about 822.96 meters (2700 feet), ie shown as n ² 6. After drilling in the n ² 6 oil production zone for about 822.96 meters (2700 feet), the side directional drilling drilled through a zone of low water saturation for about 304.8 meters (1000 feet) n ² 7. At the end of the side directional drilling, the oil production zone was reentered for about 152.4 meters (500 feet) n ² 8. The pit track on the side n ² 9 shows that the deepest part of O was at the beginning of the side. The side continued to drill more shallow and remained in the n ² 6 oil production zone until the unfinished well became sufficiently shallow so that the side was no longer drilling in the n ² 6 oil production zone, but that drilling additional area above the oil production zone and in the shallower water segment n ² 7. Towards the end of the side drilling, the well track deepens again, as shown towards the end of n ² 9. The new deepening results in the unfinished well re-entering the oil production zone as n ² 8, as revealed by the water saturated curve with oil n ² 5.
[225] A stylized / simplified representation of certain elements of this data is provided in Figure 4b. Specifically, the vertical zones of water n ² 3, oil n ² 2 and water zones n ² 4 are plotted with water saturated with oil n ² 15 along well track n ² 9 that identifies lateral zones of oil n ² 6 , water n ² 7 and oil n ² 8. This reflects the ability of the methods of the present invention to be applied to
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133/164 wells that have both vertical and lateral characteristics and provide “data maps in both directions, even in a single well or area.
[226] This example demonstrates that the methods of the invention can allow the collection of data in real time at the site of a side being drilled, so that this data in real time can be used to help “lead (direct, guide) the towards the side, in order to keep the well unfinished in or very close to the oil production zone.
EXAMPLE 5 [227] This Example demonstrates the application of a method of this invention to distinguish between oil production zones and gas zones at a well site.
[228] In this Example, 205 sealed oil well cut samples were subjected to analysis as described above. Three aliquots were obtained from each sample, under different pressures (25 millibar, 1 millibare 0.1 millibar).
[229] SW was calculated from conventional petrophysical data, indicating the presence of hydrocarbons in the geological formation at the site. However, SW cannot distinguish between water and gas deposits, as discussed above.
[230] The results of the various data obtained by the performance of the method, such as information on acetic acid and formic acid, are plotted in Figure 5. A stylized interpretation of these data is shown in Figure 5B using the same numbering scheme as in Figure 5 .
[231] A post-drilling assessment of the target indicated that the well under analysis in this example was a gas well and as such was not economical and was abandoned. Conventional well profiles indicated a large production area n ² 1 of several hundred
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134/164 feet of overlapping thickness ² 2 and sustained ² 3 by strata that have high water saturations. The well was drilled and tested at about the average depth of the production area. The well flowed gas. At this point, the operator abandoned the well, believing that the production area was entirely gas.
[232] Analyzes using the methods of the invention, however, indicate that the bottom at 60.96 meters (200 feet) of the production zone was oil n ² 7. This determination was based on high responses of total oil n ² 4, high responses of acetic and formic acid n ² 5 and high water saturated with oil n ² 6. The remaining production zone above oil production is then gas n ² 8, as tested. Above gas are strata with high water saturation n ² 9, and below oil production are strata with high oil saturation n ² 10.
[233] The data shown in Figures 5 and 5B demonstrate that derived cutting data obtained by applying the methods of the invention can distinguish between oil and gas production zones, which is of significant economic importance.
[234] The data shown above demonstrates that the derived shear data obtained by applying the methods of the invention can distinguish between oil and gas deposits and can also confirm conventional core analysis information. Since conventional core analysis is significantly more expensive and takes longer than the cut analysis of the invention, it provides yet another important benefit of the methods of the invention.
EXAMPLE 6 [235] The methods of the invention can be applied to large regional areas or wells that span large regional areas to provide plots of entire interregional fields, regions or wells. The identification of acetic acid and / or formic acid and / or water saturated with oil in cuts may indicate that, although a well in question is
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135/164 a “dry hole (a well that does not produce appreciable quantities of oil or gas), the well is, however, in proximity to a field. These data can then be used as a means to guide exploration of the well site in terms of lateral drilling or drilling of new wells nearby. A simple and stylized version of a data plot that could be obtained from carrying out such an analysis is shown as Figure 6.
[236] More specifically, Figure 6 provides a simplified two-dimensional representation of a large conventional gas field. A permeable sandstone reservoir rock has undergone deformation in order to have a suitable structure to trap n ² 1 oil. The n ² 1 sandstone reservoir is overlaid by a shale that has low permeability n ² 2 that acts as a seal. The gas migrated to the sandstone reservoir n ² 1 from a deeper source and now fills the sandstone to the contact between gas and water (GWC) n ² 3. The shallower sandstone that the GWC is charged with gas. The pores in the sandstone, which are deeper than the GWC, are filled with water. Formic and acidic acids occur in moist oils and gases and can be partitioned from the gas and oil phase into the water phase. These light carboxylic acids are miscible in water. One aspect of the invention is the perception that the measurement of high amounts of these acids in formation waters in permeable reservoir formations filled with water indicates proximity to large economic production zones in conventional oil and gas production n ² 6. In non-reservoirs Conventional with very limited permeability, oil and gas coexist in close contact with high amounts of formation water, and often, in these cases, the proximity to production which indicates that acids occur in high quantities within the production area itself. This is the case in the previous examples. However, in this example of high permeability
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136/164 conventional, gas and water are able to segregate into separate separate zones as controlled by gravity separation.
EXAMPLE 7 [237] This example provides the results of analysis performed with wet reservoir sands directly below two small local oil production zones, as well as two wet sands that are in the downward direction of the formation dip in a giant gas reservoir , as shown in Figure 7. The resistivity profile indicates two small non-economic production zones in this well, n ² 2 and ² 3. Five rectangular boxes, n ² 4a and ² 4e, are the sandstone bodies in this well, as indicated by the gamma ray profile. The rest of the penetrated strata represented here are shales. Sands n ² 4a and ² 4e have small oil segments on top of the sands and are moistened with water below the oil. The sands n ² 4c and n ² 4d are moistened with water, but are continuous to sands from reservoir to a giant gas field at the top of the dive. Sand n ² 4b is moistened with water and has no production at the top of the dive. The acetic acid information is plotted against a resistivity profile. These data provide not only information on the presence of oil production zones, but mapped against the nature of the material, they also reflect where on the site the best economic dividend could be provided.
[238] It may be advantageous to relate the methods and results of this example to the disclosures in Example 6 and Figure 6, because the material in this Example contains thick water-loaded sandstone that has low resistivity and is located about half a mile laterally. and at 152.4 meters (500 feet) in the downward direction of the formation dip to a large n ² 1 gas field that produces from the same sandstone formation. There are no seals between the gas field and this dry hole. Sandstone, which is the
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137/164 source / cause of the dry hole, is in good permeable communication with the same formation of sandstone in the accumulation of giant gas, as shown in Figure 6.
[239] Although this sand is completely charged with water and shows low resistivity at this location, the entire sandstone body shows high levels of acetic acid, which, according to one aspect of the invention, are indicative of proximity to the nearby giant gas field n ² 1 in Figure 7. If this well was drilled before the nearby giant field was revealed, conventional profiles and other types of conventional analyzes that could have previously been applied commonly to these samples, no indication could be given that this well is in close proximity to the giant gas field. However, the high anomalies of acetic acid n ² 1 in these wet sands n ² 4c and ² 4d, provide a unique indication of the existence of a large accumulation of near oil. This data could also strongly support exploration in this area.
[240] There is another sand in Figure 7 that is moistened with water and contains no production n ² 4b. The contents of sand acetic acid 4b are similar to the shales surrounding above and below it. From other wells drilled in this area, it has been known that sand 4b is not loaded with gas or oil at the top of the dive to this location. The low levels of sand acetic acid n ² 4b in relation to the obviously higher concentrations of acetic acid in zones n ² 4c and ² 4d provide a local calibration that indicates the importance of acetic acid in sands n ² 4c and ² 4d in relation to to analyze the characteristics of the material / training.
[241] There are more sands n ² 4a and ² 4e in which the resistivity profile indicates that they have small production areas at the top of each sand. In each of these sands with smaller production zones n ² 4a and ² 4e, anomalies of acetic acid n ² 5a for sand n ² 4a and ² 6a for sand n ²
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4e can be seen. A very interesting aspect of anomalies of acetic acid n ² 5a and ² 6a is that they also occur only near the top of each sand. The anomaly of acetic acid for sand n ² 4c and n ² 4d is high for the entire sand body. This is the situation that was expected for a sand as shown in Figure 6, where the entire body of sand is loaded with oil or gas a high part of the dive to this location. Diffusion and flow of fluids in geological formations are usually much easier together with stratification than cross-stratification. Therefore, the fact that the whole sands n ² 4c and ² 4d show high levels of acetic acid is an indication that these sands are fully loaded at some distance in a high part of the dive, and are. On the other hand, the fact that sands n ² 4a and ² 4e show anomalies of acetic acid only at the top of the sands is an indication that this is a small oil deposit of only local extent and may be of low economic interest or even insufficient in relation to drilling. Acetic acid is observed only directly adjacent to small oil columns seen in the resistivity profile as n ² 5a and ² 6a. The majority of each n ² 4a and ² 4e sand lacks any anomaly of acetic acid as shown by the lower portions of each sand as n ² 5b and ² 6b.
[242] This data reflects that one aspect of the invention is the use of acetic acid data derived from geological formations to classify the analyzed sands. Sand n ² 4b does not show an increase in acetic acid in relation to shales immediately above and below, and therefore sand n ² 4b was determined to be without prospect, and data from surrounding wells support this interpretation. There are only anomalies of acetic acid very much located on the top of sands n ² 4a and ² 4e, and these data indicate that these anomalies of acetic acid n ² 5a and ² 6a are local in nature and not indicative of
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139/164 next economically significant production. On the other hand, the totality of sand n ² 4c and ² 4d shows high levels of acetic acid. Although the magnitude of the anomaly in sand n ² 4a is higher than in sand n ² 4c and ² 4d, the fact that anomalies in n ² 4c and ² 4d cover the entire sand, while anomalies in sand n ² 4a en ² 4e cover only the top of the sands, it is indicative that the anomalies n ² 4c and n ² 4d are related to / are indicative of large production areas and probably economically significant, in contrast to the implications derived from the more limited anomalies in the sand n ² 4a en ² 4e. Thus, this Example demonstrates how the methods of the invention can be used to “map or characterize the entire geological structure or region in relation to the proximity to the oil production zones in the structure / region.
EXAMPLE 8 [243] Plots were obtained from the performance of the methods described above for a “dry gas” site and a “wet gas” site. The results of these analyzes are shown in Figures 8A and 8B. A stylized interpretation of this data is shown in Figure 8C. This analysis reflects the ability of the invention's methods to distinguish between the nature of various target sites.
[244] In Figure 8a, a depth of dry gas anomaly in the well is dominated by methane n ² 1, ethane n ² 2 and propane n ² 3. Higher liquid hydrocarbons are essentially absent, with the exception of a residual amount of benzene n ² 4 that can hardly be seen. Curve No. ² shows the total amount of ethane that could be produced from a standard perforated side about 1371.6 meters (4500 feet) long with a production radius of about 15.24 meters (50 feet) . The analyst can calculate this number since the number of nanomoles of the gases to be analyzed can be determined since the results are
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140/164 quantitative and referring to analytical standards, and the sample volume analyzed is kept constant at 400 microliters of rock for each sample. The result shown as curve n ² 5 is simply the result of scaling up the data by how much ethane in volume the analytical results are equivalent to a volume of cylindrical rock that is 1371.6 meters (4500 feet) long with a radius 15.24 meters (50 feet).
[245] Figure η ² 8B is plotted on the same scale as Figure n ² 8A. As shown, there is much less methane n ² 1, ethane n ² 2 and propane n ² 3 here. In addition, the data reflects that there is much more liquid hydrocarbon than seen in the data in Figure 8A. C4-C8 paraffins are shown as n ² 4 an ² 8, C6 to C8 naphthenes are shown as n ² 9 an ² 11, and aromatic C6-C8 are shown as n ² 12 an ² 14. The trail that shows predicted ethanol production n ² 15 is insignificant compared to the same n ² 5 rail in Figure 8A plotted on the same scale. However, the predicted liquid production is much higher in Figure 8B than in Figure 8A. Both Figures 8A and 8B represent unconventional wells in which the source rock is also the reservoir after hydraulic fracturing. The source rock in the well shown in Figure 8A was buried at much greater depths and thus generated much drier gas than the source rock in the well shown in Figure 8B. The gaseous compositions derived from these analyzes thus provide information on the burial history of the target formations, which are an essential part of the information in oil exploration, for both conventional and unconventional reserves.
[246] This situation is shown in the simplified diagrams in Figure 8C. The drier gas shown as n ² 1 is produced from the source rock that has experienced much higher temperatures for much longer periods of time than the wet gas shown as
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141/164 η ² 2.
[247] This data can be used to solve a variety of geological problems, especially when combined with other information from a variety of sources.
[248] The analysis can and will often be applied to relatively larger hydrocarbons, such as up to C10 hydrocarbons, but the C9 and C10 data obtained in this work have been omitted from Figures 8a and 8b for the sake of clarity. Since Figures 8A and 8B are plotted on the same scales, it is evident that the gas in the well in Figure 8A is much drier than the gas in the well in Figure 8B. This Example reflects several aspects of the invention - from producing patterns to using such patterns or, more generally, comparing data from different well sites to characterize a geographic / geological area of multiple wells.
EXAMPLE 9 [249] The methods of the invention could be applied to map regions, as noted elsewhere in this document. An illustration of the concept is shown in Figure 9. Figure 9 provides an example of what the output of such a regional mapping of oil well sites might look like conceptually, providing areas of high oil n ² 1 indications and / or other information, such as porosity, which could be used to provide favorable drilling site maps and also used to predict other less prospective sites versus areas of low oil n ² 2 indications or areas of low proximity to production indications, or other indications from data that can attest to the high or low proximity of finding oil and / or gas.
EXAMPLE 10 [250] In this Example, the data was gathered in a similar manner to the protocols described in Examples 2 to 4. The data obtained
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142/164 from this analysis are shown as Figure 10 and an interpretation of the data is provided as Figure 10A.
[251] The well represented in Figure 10 was drilled to a deeper target and there was no effort spent searching for production zones in the shallowest part of the well represented in Figure 10. However, the sample analyzes shown in Figure 10 revealed a 182.88 meters (600 feet) oil column that was indicated for high content of water saturated with oil n ² 1 and high contents of formic acids and acid n ² 2. As discussed above, in unconventional reservoirs that have very high permeability low, one or more indicators of proximity to production, for example, formic and acetic acids, can delineate the production zone and both water and oil coexist in the same strata in an unconventional reservoir, and do not separate into production zones discrete oil versus water segments as in many more permeable conventional reservoir environments.
[252] The 182.88 meter (600 ft) column detected by water saturated with n ² 1 oil and n ² 2 organic acids is actually two oil piles that are juxtaposed on top of each other. The analysis of the data allows the discrimination of these two oils as having different chemical compositions using the paraffin curves / (paraffins + naphthenes) and the aromatics / aromatics + naphthenes) n ² 3, with relatively low values for both these reasons at 121.92 meters (400 feet) higher than the production zone n ² 3 that was identified using water saturated with oil n ² 1 and organic acids n ² 2. However, data n ² 4 shows high values of these ratios for 60.96 meters ( 200 feet) deeper from this production zone. The data indicates to those skilled in the art that the oil in the upper zone n ² 3 is heavier than the oil in the lower zone n ² 4. This is somewhat unusual if this were an oil and gas reservoir system
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143/164 conventional, as in those systems in which oil and gas become stratified by gravity according to density, that is, in conventional reservoirs, oil is usually stratified with the lightest oil above the heaviest oil. This, however, is not a trend that is particularly relevant in unconventional reservoirs with very small permeability. In this case, the data obtained by the method of the invention indicate that reservoir n ² 3 is a poorly permeable carbonate to which oil and reservoir gas migrated from some source rock that is spatially removed from the reservoir. Reservoir n ² 4 in contrast is a shale rich in organic product that is both the source for the oil it retains and the reservoir for the oil. Non-conventional source rock oil tends to be lighter than migrated oil. The migrated oil tends to lose lighter hydrocarbons during the expulsion of the source rock, that is, primary migration, and transportation to the reservoir, that is, secondary migration, and during the permanence of the oil in the reservoir. Since poorly permeable shales can be both the source and the reservoir, oil in poorly permeable shales does not lose its most volatile components during migration while they are in the reservoir and, therefore, is usually lighter than conventional oil. Therefore, it is reasonable to conclude that the overlying oil n ² 3 in a low-permeable limestone is heavier than the underlying oil in a shale rich in low-permeable organic products.
[253] From a production point of view, reservoir n ² 3 and reservoir n ² 4 will need to be produced as separate reservoirs. Reservoirs n ² 3 and ² 4 are not in communication. They will produce different types of oil. And various aspects of the reservoir, such as hydrostatic pressure, will be different. This reflects an advantageous element of the invention in identifying and characterizing separate production areas with separate characteristics.
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144/164 [254] Figure 10A illustrates other aspects of this Example. The n ² 1 curve on the left is the resistivity curve that indicates an oil column of 182.88 meters (600 feet) covered and supported by water, as shown by the product type profile n ² 2. The oil column of 182.88 meters (600 feet) n ² 1 is shown to be divided into an upper heavier oil reservoir 400 feet thick and a light oil reservoir 121.92 meters (200 feet) deep n ² 4 The distinction between n ² 3 shallow heavy oil reservoir and n ² 4 deeper lighter oil reservoir is based on the paraffin / naphthene n ² 5 ratio curve and the aromatic / naphthene n ² 6 ratio curve.
[255] The results of this analysis demonstrate that the methods of the invention as exemplified here can identify two separate oil production zones and further demonstrate that the cutting analysis methods of the invention can be used to distinguish between different types of oil zones. oil production at a well site, which could otherwise be confused with each other based on other methods of analysis.
EXAMPLE 11 [256] The methods of the invention can be performed to demonstrate different zones of oil production in one site due to the presence of different hydrocarbon profiles present in the respective sites. In this respect, the methods of the invention could be used to identify discrete and compartmentalized oil production zone sites. A reflection of this concept is provided in Figure 11.
[257] As shown in Figure 11, Well A n ² 1 and Well B n ² 2 are both oil wells drilled in similar geological situations. The oil production zone in Well A n ² 3 is oil comprised of high levels of paraffins and aromatics, but low in
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145/164 naphthenes. The oil production zone at Well B n ² 4 contains oil comprised of high levels of paraffins and aromatics, but also a high content of naphthenes. The oil in the reservoir n ² 3 will have a different character than the oil in the reservoir η ² 4. Documenting the difference using data obtained by the methods of the invention described in this document, then, will allow those trained in the oil exploration technique to consider various scenarios for represent this observed difference. In addition, the recognition that two different oils occurring in an area reduces the risk of exploration in that area as the probability of finding oil is increased if there is more than one oil source that can fill reservoirs in the area that is explored.
EXAMPLE 12 [258] This Example provides an illustration of a method for measuring the many parameters described above associated with a sample to characterize a material in a well site device according to certain aspects of the invention, wherein the method of the invention involving the use of the device occurs while the well is being drilled at such a rate so that the data is obtained as quickly as possible so that this data can be used to assist in “driving the well in a manner close to“ real time ( it is expected that there will often be a “delay of about 3.05 to 30.48 meters (10 to 100 feet), such as about 6.1 to 18.29 meters (20 to 60 feet), from the active drilling site and the last data analysis site, given simply the logistics of well operations, such as limitations on what can be placed in a drill bit, noise and interfering and movement, etc.). Aspects of the invention, such as the device and method provided herein, can be advantageous for the ideal positioning of lateral wells, also known as horizontal wells.
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146/164 [259] A device for a rapid method for determining fracture at the pit site is shown in Figure 12. With reference to the device in Figure 12, n ² 1 represents the discharge of mud and flow line cuts and for the sludge receiving tank from a conventional oil well. A reusable deformable container, n ² 2, is positioned so that a portion of the mud discharge and flow cuts need to flow through it. A screen, n ² 4, is placed at the bottom of the reusable deformable container, n ² 2, which allows drilling mud to escape from the deformable reusable container n ² 2, but keeps the n ² 3 cuts inside the container. An air piston, n ² 5, is located outside the discharge of mud and cuts n ² 1. Air piston n ² 5 transmits unidirectional force to crush the cuts n ² 3 through the elongated rod n ² 6. A rotating device , n ² 7, usually activated by air pressure, rotates the screen n ² 4 using the rod n ² 8 away from the deformable container n ² 2 to discharge material from the n ² 3 cuts after they have been crushed. The screen n ² 4 is retracted from the reusable deformable container n ² 2 for a sufficient amount of time to allow the now crushed cuts n ² 3 to be removed from the deformable chamber n ² 2 to be cleaned from the chamber by the vigorous flow of mud and cuts n ² 1. Device n ² 7 could be another air piston that moves the screen sideways out from under the reusable deformable container n ² 2 instead of a rotating device.
[260] The top view shows that the reusable deformable container n ² 2 is comprised of two parts. The part n ² 9 has a U shape in cross section, having two right angle edges. The fourth wall of the reusable deformable container is a plate No. ² 10 which has no solid connection to the portion No. ² of the container. By filling the reusable deformable container n ² 9 en ² 2 with n ² 3 cuts from the mud discharge and n ² 1 mud line cuts, the cuts are crushed by activating the air piston n ² 1 to tighten
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147/164 the same through the transmission of a force through stem n ² 11 to plate n ² 10. The fracturability of the cuts is determined by measuring and recording how much stem n ² 11 has been extended from the air piston n ² 12. The speed and fluidity of movement of the crushing of the n ² 3 cuts can also be recorded, as well as any recovery of the crushing assembly by releasing force on the air piston n ² 12. These parameters can assist in a more complete description of the mechanical properties of the cuts, including Poisson's ratio and Young's modulus. These parameters, together with fracturability, can be important and useful for directing a side to remain on rocks of ideal mechanical strength and for determining the best way to complete the side through the stages of fracturing and oil production.
LIST OF ILLUSTRATIVE ASPECTS OF THE INVENTION [261] The following is a non-limiting list of certain aspects of the invention that may provide additional assistance and guidance in understanding the unique features and advantages that the invention provides.
[262] The first set of aspects refers to methods in which multiple aliquots are obtained from a sample and the volatile substances in such aliquots analyzed:
[263] 1. A method for analyzing volatile substances in a material comprising: - [264] a. Provide an analyzable sample of a material [265] b. Subject the sample to one or more forces to release a first gas containing an analyzable amount of one or more volatile substances, [266] c. Trap and concentrate the gas in or with a medium in an analyzable amount to generate an aliquot,
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148/164 [267] d. Isolate the aliquot from the sample, [268] e. Release volatile substances from the rate as gases released in a predictable sequence, [269] f. Analyze the volatile substance chemistry of at least one of the volatile substances to obtain an aliquot analysis, [270] g. Carry out at least one analysis cycle comprising the repetition steps b to f of the method, at least one additional time, in which, for each repetition, the specific force applied is different from the force previously applied to the sample and [271] h. Analyze all analyzes to provide information about the material.
[272] 2. The method of aspect 1, in which one or more forces comprise subjecting the sample to a specific pressure without mechanical rupture, for example, crushing.
[273] 3. The method of aspect 2, in which the sample is initially subjected to the specific pressure in which it was sealed in its container so that no unsealed volatile product is lost. This is usually done at about 1 to 100 millibar, such as 2 to 80 millibar, for example, about 3 to 75 millibar.
[274] 4. The method of any of aspects 1 to 3, in which the sample is subjected to the specific pressure and temperature at which it was initially obtained.
[275] 5. The method of any one of aspect 4, wherein the method comprises subjecting the sample to different pressures, without mechanical rupture.
[276] 6. The method of any of aspects 1 to 5, in which the analysis of volatile substance chemistry comprises subjecting the volatile substances to mass spectrometry.
[277] 7. The method of any of aspects 1 to 6, in which the analysis provides information regarding the quantity of one or more
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149/164 volatile compounds in the material.
[278] 8. The method of any one of aspects 1 to 7, where step h of the method (the analysis step) comprises comparing at least some of the analyzes against one or more standards.
[279] 9. The method of any one of aspects 1 to 8, in which the force comprises dehydrating the sample before crushing, applying mechanical pressure to the sample, mechanically breaking part or all of the sample, subjecting the sample to a chemical reaction or a combination of any of them.
[280] 10. The method of any of aspects 1 to 9, in which the method also comprises subjecting the sample to two or more different pressures, optionally to generate two or more aliquots. [281] 11.0 method of any of aspects 1 to 10, wherein the volatile substances comprise C1-C20 hydrocarbons.
[282] 12. The method of any of aspects 1 to 11, in which the trapping step comprises subjecting the gas to a non-selective trapping.
[283] 13. The method of any of aspects 1 to 12, in which the trapping step comprises cryogenic capture of the gas.
[284] 14. The method of aspect 13, wherein the trapping step comprises subjecting the gas to temperatures below about -50 degrees C.
[285] 15. The method of aspect 14, in which the method comprises putting the gas in contact with a material cooled by contact with liquid nitrogen.
[286] 16. The method of any of aspects 1 to 15, wherein the volatile substances comprise C1-C10 hydrocarbons.
[287] 17. The method of any of aspects 3 to 16, in which the pressure is positive pressure of ambient atmospheric pressure in excess of ambient atmospheric pressure or a vacuum level below
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150/164 atmospheric pressure, but greater than 3x10-4 millibar.
[288] 18. The method of aspect 17, in which the pressures applied to the sample are greater than 1 x 10 -3 millibar.
[289] 19. The aspect 18 method, where the pressures applied to the sample are greater than 25 x 10 -3 millibar.
[290] 20. The method of aspect 19, in which the pressures applied to the sample are greater than 1 x 10 -2 millibar.
[291] 21. The method of any of aspects 3 to 20, wherein the method comprises subjecting the sample to a pressure between 1 to 100 millibar.
[292] 22. The method of any one of aspects 1 to 21, in which the sample is a rock that does not comprise recent fluid inclusions that could have recently trapped fluids, such as current oil and / or gas.
[293] 23. The aspect 22 method, in which the sample did not experience significant burial diagenesis.
[294] 24. The method of any one of aspects 1 to 23, wherein the method comprises removing potentially interfering gases from contact with the medium before analyzing the gases released from the aliquot.
[295] 25. The method of aspect 24, in which the interfering gases removed comprise oxygen, nitrogen or both oxygen and nitrogen.
[296] 26. The method of aspect 25, in which the method comprises purging oxygen and nitrogen from contact with the medium by contact with an inert gas that does not chemically react with the sample and does not cause any interference in the chemical analysis of volatile products from samples.
[297] 27. The method of aspect 26, wherein the inert gas is an inert gas, such as argon or nitrogen.
[298] 28. The method of any of aspects 1 to 27, in which
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151/164 more than 50% of the volatile substances in the sample are analyzed by the method.
[299] 29. The aspect 28 method, in which more than 75% of the volatile substances in the sample are analyzed by the method.
[300] 30. The Aspect 30 method, in which more than 90% of the volatile substances in the sample are analyzed by the method.
[301] 31. The aspect 30 method, in which more than 99% of the volatile substances in the sample are analyzed.
[302] 32. The method of any of aspects 1 to 31, in which the first gas is allowed to come in contact with the medium for 0.1 second to 10 minutes.
[303] 33. The method of any of aspects 1 to 32, in which the first gas is allowed to come in contact with the medium for about 10 minutes or more.
[304] 34. The method of aspect 33, in which the first gas is allowed to come in contact with the medium for about 20 minutes or more.
[305] 35. The method of aspect 34, in which the first gas is allowed to come in contact with the medium for about 40 minutes or more.
[306] 36. The method of any of aspects 1 to 35, wherein the method does not comprise heating the sample to temperatures greater than 100 O.
[307] 37. The method of aspect 36, wherein the method does not comprise heating the sample to temperatures greater than 60 O.
[308] 38. The method of any one of aspects 1 to 37, wherein the method comprises collecting a portion of the first gas from at least one of the cycles that will not bind to the medium as a separate non-condensable gas and submitting this rate of non-condensable gas for separate analysis.
[309] 39. The method of aspect 38, in which the medium is a frozen surface to which the first gas condenses and at least part of the portion
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152/164 will not condense on the cooled surface.
[310] 40. The method of aspect 38 or aspect 39, wherein the method comprises isolating non-condensable gas from condensable gases to facilitate separate analysis thereof.
[311] 41.0 method of any of aspects 38 to 40, wherein the portion of the non-condensable gas comprises methane, helium, hydrogen or a combination of part or all of them.
[312] 42. The method of any of aspects 38 to 41, wherein the portion of the non-condensable gas comprises neon, argon, krypton or a combination of two or more of these gases.
[313] 43. The method of any one of aspects 1 to 42, wherein the method comprises containing the sample in a container that isolates the sample from the environment in a way that substantially retains the volatile substances in the sample from the moment the sample is placed in the container until the first gas is released.
[314] 44. The method of aspect 43, wherein the container comprises a seal that can be selectively perforated to release the first gas, allowing the gaseous content of the container to flow into contact with the medium when pierced.
[315] 45. The method of aspect 43, wherein the container comprises a connector system without perforation.
[316] 46. The method of any one of aspects 1 to 45, wherein the method comprises collecting the first gas under each different condition for at least about 1 minute to form each aliquot.
[317] 47. The method of any one of aspects 1 to 46, wherein the method comprises the step of substantially removing one or more potentially interfering gases before trapping the first gas.
[318] 48. The method of aspect 47, in which the step of removing potentially interfering gases is completed in about 3 seconds
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153/164 or less.
[319] 49. The method of aspect 47 or aspect 48, in which the potentially interfering gases comprise oxygen, nitrogen, carbon dioxide or a combination thereof.
[320] 50. The method of aspect 47 or aspect 49, wherein the method comprises purging the potentially interfering gas from contact with the medium by filling the area surrounding the medium with a purging gas, such as a non-condensable gas .
[321] 51. The method of aspect 50, in which the purge gas is argon or krypton.
[322] 52. The method of any of aspects 1 to 51, in which the medium is a cooled surface.
[323] 53. The aspect 52 method, in which the surface is cooled by direct contact with liquid nitrogen or other cryogenic liquid, such as liquid argon, liquid oxygen or liquid helium.
[324] 54. The method of any of aspects 1 to 53, wherein the method comprises performing an optional analysis at atmospheric pressure and at least two analyzes at different pressures, both of which are below atmospheric pressure.
[325] 55. The method of any of aspects 1 to 54, in which the method does not include performing gas chromatographic analysis.
[326] 56. The method of any of aspects 1 to 55, in which the method comprises assessing the permeability of the sample by assessing differences in the rates obtained by extraction under two sets of different conditions.
[327] The following listing of aspects of the invention is directed to a method of the invention which comprises extracting and analyzing only a single aliquot of material:
[328] 57. A method for analyzing volatile substances in a material comprising:
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154/164 [329] a. Provide an analyzable sample of a material [330] b. Subject the sample to one or more forces to release a first gas containing an analyzable amount of one or more volatile substances, [331] c. Trap and concentrate the first trapping gas (such as a condensable gas in a system based on gas condensation) in or with a medium in an analyzable amount to generate an aliquot, [332] d. Isolate the aliquot from the sample, [333] e. Release volatile substances from the rate as gases released in a predictable sequence and [334] f. Analyze the volatile substance chemistry of at least one of the volatile substances to obtain an aliquot analysis.
[335] 58. The Aspect 57 method, where the method comprises only forming and analyzing a single rate, which may comprise two or more sub-rates.
[336] 59. The method of aspect 58, wherein the single rate comprises a condensable gas component that is trapped with a first trap and a non-condensable gas component that is collected separately.
[337] 60. The method of any of aspects 57 to 59, wherein the method comprises subjecting the sample to at least a pressure of at least 1 millibar and less than 1 atmosphere.
[338] 61. The method of aspect 60, wherein the method comprises subjecting the sample to a pressure of about 1 millibar to about 100 millibars.
[339] 62. The method of any of aspects 57 to 61, in which the sample is subjected to vacuum pressure for a period of about 0.25 minutes to about 15 minutes.
[340] 63. The method of any of aspects 57 to 62, in which
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155/164 to one or more forces comprises subjecting the sample to a crushing force in addition to one or more other forces, such as vacuum pressure, vibration energy or radiation energy, such as laser excitation, or a combination of any one or all of them.
[341] 64. The method of any of aspects 57 to 63, wherein the analysis of volatile substance chemistry comprises subjecting the volatile substances to mass spectrometry or another method of analysis.
[342] 65. The method of any of aspects 57 to 63, wherein the trapping step comprises cryogenic capture of condensable gas and, optionally, capture of a sub-aliquot of non-condensable gas in a separate way for separate analysis.
[343] 66. The method of any of aspects 57 to 65, wherein the method comprises removing potentially interfering gases from contact with the medium before analyzing the gases released from the aliquot.
[344] 67. The method of any of aspects 57 to 66, in which the method does not comprise heating the sample to temperatures greater than 100Ό.
[345] 68. The method of any of aspects 57 to 67, wherein the method comprises measuring the ductility of the sample by supplying the sample in a crushable container and determining the size of the impact of the crushing force on the container and the sample.
[346] 69. The method of any of aspects 57 to 68, wherein the method comprises collecting and sealing the samples in the wells versus samples loaded in the laboratory.
[347] 70. The method of any of aspects 57 to 69, in which the method comprises collecting and analyzing samples in close proximity to the well site.
[348] 71. The method of any of aspects 57 to 70, in which
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156/164 the method comprises collecting and analyzing samples within a well, such as a well that is under active drilling.
[349] 72. The 71 aspect method, where the method comprises real-time or near real-time analysis of samples, for example, where the delay time between the drilling site and the analysis of samples is less than about 15.24 meters (50 feet), such as less than about 12.19 meters (40 feet), less than about 9.14 meters (30 feet), less than about 6.1 meters (20 feet) ) or less than about 3.05 meters (10 feet), 2.13 meters (7 feet), 1.52 meters (5 feet) or even less than about 0.3 meters (1 foot).
[350] 73. The method of any of aspects 57 to 72, wherein the method comprises measuring the amount of acetic acid, formic acid and / or water saturated with oil associated with the sample.
[351] 74. The method of any of aspects 57 to 73, wherein the method comprises measuring the amount of methane, carbon dioxide and / or carbon monoxide that is released from entrapment.
[352] 75. The method of aspect 74, wherein the method comprises measuring the amount of carbon monoxide that is released from entrapment.
[353] 76. The method of any of aspects 57 to 75, in which one or more steps of the method are carried out in close proximity to an oil well site.
[354] 77. The aspect 76 method, where the method is performed within about 45.72 meters (150 feet) of the drilling site.
[355] 78. The 77 aspect method, where the method comprises pneumatic distribution of samples to a laboratory for analysis.
[356] 79. The Aspect 78 method, where the method comprises real-time analysis while the well is being drilled, and data is used to direct the well and keep the well unfinished in or as close as possible to the production zone target.
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157/164 [357] In general, aspects that are dependent on aspect 57 can apply to the method of aspect 1. Aspects that are dependent on aspect 1 can be applied to aspect 57. In fact, aspect 1 can be considered dependent on aspect 57. Any of these methods reflected in aspects 1 to 79 can comprise developing a pattern and / or adjustments for conditions at a location (for example, calculating the carbon monoxide located at a location and subtracting it from an amount measure or apply an approach similar to formic acid, acetic acid and / or water saturated with oil).
[358] The following set of aspects is directed to a method focused on evaluating mainly the ductility (fracturability) of a material by performance of a method of the invention:
[359] 80. A method for analyzing the ductility or hardness of geological formation which comprises:
[360] a. Provide an analyzable sample of a material, [361] b. Subject the sample to one or more forces that are capable of compressing the material of a given hardness or ductility and [362] c. Determine the amount of compression of the sample.
[363] 81. The aspect 80 method, wherein the method comprises compressing multiple sides of the sample simultaneously.
[364] 82. The method of aspect 81, wherein the method comprises isotopically compressing the sample.
[365] 83. The method of any of aspects 80 to 82, in which the sample is obtained from an oil well.
[366] 84. The aspect 83 method, in which the sample is selected from a cut and a core sample.
[367] 85. The method of aspect 84, in which the sample is a cut.
[368] 86. The method of any of aspects 80 to 85, in which the method is performed on multiple samples from one site.
[369] 87. The aspect 86 method, in which samples
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158/164 comprise samples obtained from different depths of a material, where the depths are in the range of about 0.15 meters (0.5 feet) to about 30.48 meters (100 feet).
[370] 88. The Aspect 86 or Aspect 87 method, in which the samples comprise materials obtained from approximately the same depth zone, but from locations that are approximately 0.15 meters (0.5 feet) apart about 30.48 meters (100 feet).
[371] 89. The method of any of aspects 86 to 88, wherein the method comprises analyzing at least 10 samples of different depths.
[372] 90. The method of any of aspects 86 to 89, wherein the method comprises analyzing at least 10 samples from the same depth zone.
[373] 91. The method of any of aspects 86 to 90, wherein the method comprises analyzing about 10 to about 2500 samples.
[374] 92. The method of any of aspects 80 to 91, where the method comprises combining the results of the method with the results of mineralogical analysis of the sample, other samples or of the material, X-ray diffraction of the samples, other samples or the material; X-ray fluorescence of the samples, other samples or the material; a measurement of total organic content associated with the samples, other samples or the material and / or combination with other data, such as photography and / or spectroscopy of the samples or other samples or the material by any suitable means at any wavelength and / or chemical, geochemical or material testing of samples, related samples or material, or a combination of any or all of the same.
[375] The following set of aspects is directed to a device of the invention for the analysis of oil saturation and / or water saturation of the samples:
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159/164 [376] 93. A device comprising:
[377] (a) a chamber for receiving and isolating samples of a material [378] (b) a detection component capable of detecting the amount of one or more target volatile substances released from the sample, where the substance comprises carbon monoxide , acetic acid, formic acid, or a combination thereof, optionally in combination with hydrocarbons, inorganic gases or a combination thereof.
[379] 94. The device of aspect 93, wherein the device comprises an energy input component that promotes the release of volatile substances from the sample.
[380] 95. The device of aspect 94, where the energy input component is (a) a pressure generating device or system, (b) a device or system that promotes the release of volatile substances through mechanical forces , thermal forces, or both, or a combination of (a) and (b).
[381] 96. The device of any of aspects 93 to 95, wherein the device comprises a system or component for isolating volatile substances released from the sample.
[382] 97. The device of any of aspects 93 to 96, wherein the device comprises a trap for collecting and releasing volatile substances.
[383] 98. The device of aspect 97, in which the trap comprises a non-selective trap, such as a trap which comprises a trap of liquid nitrogen.
[384] 99. The device of any of aspects 93 to 98, wherein the device comprises a mass spectrometer.
[385] 100. The provision of any of aspects 93 to 99, in
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160/164 that the device comprises a component or device for selectively isolating the mass spectrometer from the sample.
[386] 101. The device of aspect 100, wherein the device comprises a trapping of volatile substance and the method comprises a component or device for selectively isolating the trapping of volatile substance from the sample, the mass spectrometer or both.
[387] 102. The device of any of aspects 93 to 101, wherein the device is part of a system comprising a mechanism for determining the compressibility of the sample.
[388] The following set of aspects is directed to another type of device provided by the invention:
[389] 103. A chemical analysis device comprising: (a) a cryogenic trap, (b) a cooling component to selectively cool the cryogenic trap, (c) a heating component to selectively heat the cryogenic trap and (d ) an analytical device comprising a mass spectrometer to analyze one or more volatile substances released from cryogenic trapping.
[390] 104. The device of aspect 103, wherein the heating component is operable in a manner that provides controlled heating of the cryogenic trap to promote the separate release of two or more volatile substances from the cryogenic trap.
[391] 105. The device of aspect 103 or aspect 104, in which the device further comprises a vacuum which can promote the release of volatile substances from a material in communication with the device, in which at least one of the volatile substances can be imprisoned by imprisonment.
[392] 106. The provision of any of the aspects 103 to 105,
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161/164 wherein the device comprises one or more housing components which maintain at least an analyzable portion of the volatile substances captured by entrapment separate from the environment.
[393] 107. The device of any of aspects 103 to 106, wherein the device further comprises a component of promoting the flow of substances through the device, such as one or more selectively operable pumps.
[394] 108. The device of any of aspects 103 to 107, wherein the device comprises a component or system for capturing one or more substances that do not bind to cryogenic trapping and for separately analyzing such one or more non-binding substances .
[395] 109. The device of either aspect 103 to 108, wherein the device comprises components for delivering a cryogenic substance selected from the group consisting of liquid nitrogen, liquid argon, liquid oxygen, liquid air, liquid helium, dry ice , a dry ice slurry, normal ice, a normal ice slurry of water ice in fresh water, a normal ice slurry of water ice in a saline brine or any other natural cooling substance capable of reaching the minimum temperature required to freeze the substance (or substances) of interest in cryogenic trapping.
[396] 110. The device of any of aspects 103 to 109, in which the cryogenic state of entrapment is at least partially achieved, and the device comprises components for mechanical cooling or cooling, as can be achieved with, for example, a Kelvinator device. The Kelvinator device or other cryogenic device must be able to reach the minimum temperature required to freeze the substance (or substances) of interest in the
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162/164 cryogenic trapping.
[397] 111.0 device of any of the aspects 103 to 110, in which the device also comprises an additional mass spectrometer, a gas chromatography; an infrared spectrometer; a Raman spectrometer; or any combination of these analytical devices.
[398] In another aspect of the invention, the methods, systems and devices described above further comprise components or steps to determine the permeability of a sample, through the application of two different forces, such as two different pressures, at each sample analyzed for permeability, and analyze the difference in the release of one or more substances or classes of substances, such as hexanes, by applying different forces. Any of the 102 aspects described above can also be modified by adding such a step or including adjustments or components to practice such steps.
INCORPORATION BY REFERENCE AND INTERPRETATION [399] All references, including publications, patent applications and patents, cited in this document are incorporated into this document for reference to the same extent as if each reference were individually or specifically indicated as being incorporated by reference and was presented in its entirety in this document.
[400] The use of the terms "one / one and" one / one and "o / a and similar referents in the context of the description of the invention (especially in the context of the following claims) should be interpreted as covering the singular and the plural, except where otherwise indicated in this document or evidently contradicted by the context. The terms "that understands," that has, "that includes and" that contains must be interpreted as open terms (that is, meaning "including,
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163/164 but without limitation) unless otherwise indicated. The mention of ranges of values in this document is intended merely to serve as an abbreviated method of individual reference to each separate value that is within the range, unless otherwise indicated in this document, and each separate value is incorporated in the specification as if it were individually cited in this document. All methods described in this document may be carried out in any other appropriate order unless otherwise indicated in this document or clearly contradicted otherwise by the context. The use of any and all examples or exemplary language (for example, such as) provided in this document is only intended to further illuminate the invention and does not propose a limitation on the scope of the invention unless claimed otherwise. No language in the specification should be interpreted as indicating any element not claimed as essential to the practice of the invention.
[401] Preferred embodiments of this invention are described in this document, including the best way known to the inventors for carrying out the invention. Variations of those preferred modalities will be made evident to those skilled in the art by reading the previous description. The inventors expect those skilled in the art to employ such variations as appropriate, and the inventors intend that the invention be practiced in a manner other than that specifically described herein. Consequently, this invention includes all modifications and equivalents of the matter cited in the claims attached to it as permitted by applicable law. In addition, any combination of the elements described above in all possible variations thereof is covered by the invention unless otherwise indicated.
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164/164 way in this document or clearly contradicted otherwise by the context.

权利要求:
Claims (33)
[1]
1. Method for analyzing material from a geological formation characterized by the fact that it comprises:
The. Provide an analyzable sample of material obtained from a geological formation,
B. Subject the sample to one or more forces that are capable of compressing the material of a given hardness or ductility, and
ç. Determine the amount of compression of the sample.
[2]
2. Method, according to claim 1, characterized by the fact that the method comprises compressing multiple sides of the sample simultaneously.
[3]
3. Method, according to claim 2, characterized by the fact that the method comprises isotopically compressing the sample.
[4]
Method according to any one of claims 1 to 3, characterized by the fact that the sample is obtained from an oil well.
[5]
5. Method, according to claim 4, characterized by the fact that the sample is selected from a cut and a section of a core sample.
[6]
6. Method, according to claim 5, characterized by the fact that the sample is a cut.
[7]
Method according to any one of claims 1 to 6, characterized by the fact that the method is performed on at least 10 samples obtained from an oil well site.
[8]
Method according to any one of claims 1 to 7, characterized in that the samples comprise a plurality of samples obtained from a plurality of different depths of a material, wherein the difference in depth between each sample is at least about 15.24 centimeters (0.5 feet).
Petition 870190065695, of 12/07/2019, p. 169/203
2/7
[9]
9. Method according to any of the claims
1 to 8, characterized by the fact that the samples comprise a plurality of materials obtained from within a limited vertical zone of less than about 12.19 meters (40 feet), but from a plurality of locations within the limited vertical zone that they are horizontally separated by about 15.24 centimeters (0.5 feet) to 30.48 meters (100 feet).
[10]
10. Method according to any of the claims
1 to 9, characterized by the fact that the method comprises analyzing at least 10 samples of different depths.
[11]
11. Method according to any one of the claims
1 to 10, characterized by the fact that the method comprises analyzing at least 10 samples from within a vertical zone of less than 7.62 meters (25 feet), but which are separated from each other by a horizontal distance of at least least about 15.24 centimeters (0.5 feet).
[12]
12. Method according to any of the claims
1 to 11, characterized by the fact that the method comprises analyzing 15 to 2,500 samples, in which more than 50% of the samples are obtained from a location that differs from the location of all other samples by at least 15.24 centimeters (0, Vertical foot) and / or at least 15.24 centimeters (0.5 horizontal foot).
[13]
13. Method according to any of the claims
1 to 12, characterized by the fact that the method also comprises performing mineralogical analysis; X-ray diffraction; X-ray fluorescence; and / or measurement of total organic content; of the sample, other samples of the material or the material itself.
[14]
14. Method according to any of the claims
1 to 13, characterized by the fact that the method also comprises performing a permeability analysis in at least one of the
Petition 870190065695, of 12/07/2019, p. 170/203
3/7 samples comprising applying at least a first pressure to the sample and separately applying a second pressure to the sample, where the first and second pressures are (a) sufficiently different and (b) each commonly effective for, at least under conditions selected, cause the release of one or more different amounts of one or more target substances, and the method further comprises assessing the release of one or more target substances to assess the permeability of the sample.
[15]
15. Method according to any of claims 1 to 14, characterized in that the method is carried out on samples that are contained in a sample container that is capable of compression under one or more forces.
[16]
16. Method according to any of claims 1 to 15, characterized by the fact that the method further comprises
i. Subject a sample to one or more forces to release a first gas containing an analyzable amount of one or more volatile substances, ii. Imprison concentrate the trapping gas in or with a medium in an analyzable amount to generate an aliquot, iii. Isolate the aliquot from the sample, iv. Release volatile substances from the rate as gases released in a predictable sequence and
v. Analyze the volatile substance chemistry of at least one of the volatile substances to obtain an aliquot analysis.
[17]
17. Method according to claim 16, characterized by the fact that the rate comprises a condensable gas sub-rate that is trapped with a first trap and analyzed with a first analysis and a non-condensable gas sub-rate that is separately captured from of the first sub-tax and analyzed separately with a second analysis.
Petition 870190065695, of 12/07/2019, p. 171/203
4/7
[18]
18. Method according to claim 16 or 17, characterized in that step i of the method comprises subjecting the sample to at least a pressure of at least 1 millibar and less than 1 atmosphere.
[19]
19. Method, according to claim 18, characterized in that the method comprises subjecting the sample to a pressure of about 1 millibar to about 100 millibars.
[20]
20. Method according to claim 18 or 19, characterized in that the sample is subjected to vacuum pressure for a period of about 0.25 minutes to about 15 minutes.
[21]
21. Method according to any one of claims 16 to 20, characterized in that the analysis of volatile substance chemistry (step v of the method) comprises subjecting the volatile substances to mass spectrometry or another method of analysis.
[22]
22. Method according to any one of claims 1 to 21, characterized in that the method comprises collecting and analyzing at least 10 samples within an active oil well, such as a well that is under active drilling, and the delay distance between sample analysis and active drilling site and sample analysis is less than about 15.24 meters (50 feet).
[23]
23. Method according to any of the claims
1 to 22, characterized by the fact that the method also comprises measuring the quantity of one or more compounds selected from the group consisting of formic acid, acetic acid, carbonic acid, bicarbonate, one or more C1-C5 hydrocarbons, hydrogen, helium, nitrogen, argon, oxygen, hydrogen sulfide, carbonyl sulfide, carbon disulfide, sulfur dioxide, carbon monoxide, carbon dioxide or water, which are associated with the sample and released from the sample and detected in the performance of the method.
Petition 870190065695, of 12/07/2019, p. 172/203
5/7
[24]
24. Method for analyzing substances in a material characterized by the fact that it comprises:
The. Provide an analyzable sample of a material
B. Subject the sample to one or more forces to release a first gas containing an analyzable amount of one or more volatile substances,
ç. Trap and concentrate the first trapped gas (such as a condensable gas in a system that relies on gas condensation) in or with a medium in an analyzable amount to generate an aliquot,
d. Isolate the aliquot from the sample,
and. Release volatile substances from the rate as gases released in a predictable sequence and
f. Analyze the volatile substance chemistry of at least one of the volatile substances to obtain an aliquot analysis.
[25]
25. Method according to claim 24, characterized in that the aliquot comprises a condensable gas component that is trapped with a first trap and a non-condensable gas component that is collected separately and analyzed separately in the performance of the method.
[26]
26. Method according to claim 24 or 25, characterized in that the method comprises subjecting the sample to at least a pressure of at least 1 millibar and less than 1 atmosphere.
[27]
27. Method according to claim 26, characterized in that the method comprises subjecting the sample to a pressure of about 1 millibar to about 100 millibars.
[28]
28. Method, according to claim 26 or 27, characterized by the fact that the sample is subjected to pressure at
Petition 870190065695, of 12/07/2019, p. 173/203
6/7 vacuum for a period of about 0.25 minutes to about 15 minutes.
[29]
29. Method according to any one of claims 24 to 28, characterized in that the one or more forces comprises subjecting the sample to a crushing force on two or more sides concomitantly, in addition, optionally, to apply one or more plus other forces in the sample, such as vacuum pressure, vibratory energy or radiation energy, such as laser excitation, or a combination of any or all of the same, and the method further comprises determining the ductility or hardness of the sample by measuring sample compression due to the crushing force.
[30]
30. Method according to any of claims 24 to 29, characterized in that the analysis of volatile substance chemistry comprises subjecting the volatile substances to mass spectrometry or another method of analysis.
[31]
31. Method according to claim 30, characterized by the fact that the trapping step comprises cryogenic capture of condensable gas.
[32]
32. Method according to any one of claims 24 to 31, characterized in that the method comprises measuring the amount of one or more compounds selected from the group consisting of formic acid, acetic acid, carbonic acid, one or more C1 -C5 hydrocarbons, bicarbonate, formic acid, acetic acid, carbonic acid, bicarbonate, one or more C1-C5 hydrocarbons, hydrogen, helium, nitrogen, argon, oxygen, hydrogen sulfide, carbonyl sulfide, carbon disulfide, sulfur dioxide , carbon monoxide, carbon dioxide or water, carbon monoxide, carbon dioxide or water, released from the sample.
[33]
33. Method according to any one of claims 24 to 32, characterized in that the method further comprises performing a permeability analysis on at least one of the
Petition 870190065695, of 12/07/2019, p. 174/203
7/7 samples comprising applying at least a first pressure to the sample and separately applying a second pressure to the sample, where the first and second pressures are (a) sufficiently different and (b) each commonly effective for, at least under conditions selected, cause the release of one or more different quantities of one or more target substances, and the method also includes assessing the release of one or more target substances to assess the permeability of the sample.

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WO2018111945A1|2018-06-21|

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法律状态:
2021-10-13| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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US201662434399P| true| 2016-12-14|2016-12-14|

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PCT/US2017/065921|WO2018111945A1|2016-12-14|2017-12-12|Methods and devices for evaluating the contents of materials|

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